CS225035B1 - The reactive greens and their preparation - Google Patents

Description

COPYRIGHT CERTIFICATE DESCRIPTION 225035 (11) (Bl)

(22) Applied 19 02 82 (21) (PV 1146-82) (51) Int. Cl.3C 09 B 62/17 (40) Published 27 05 83

OFFICE OFFICE (45) Issued 15 02 86

AND DISCOVERY (75) KOHOUTEK VÁCLAV ing., CHMÁTAL VLADIMÍR RNDr. CSc., PARDUBICE,

Author of CEE ALEŠ ing., CSc., HRADEC KRÁLOVÉ, KUTHAN PETR ing.,

NEW Jl51 ing., PARDUBICE (54) Reactive greenery and method of their preparation

AND

The invention relates to reactive greens of the general formula

B-j-NH

Cl

nh-b2 e of their preparation by forming a chemical moiety of a reactive center of cyanuric chloride base with a color component of a blue hue (B, -NH2) and a colored component of yellow shade (B2-NH2). SUMMARY OF THE INVENTION The present invention relates to the use of brilliant greenish-yellow shades that produce azo dyes in which the acid component of the acid is (2,6-dihydroxypyridine-4-carboxylic acid).

2,6-pyridone derivatives have recently become an important component for the synthesis of azo dyes with brilliant greenish-yellow shades and reactive yellow-based pyridine-2,6-dione, irreplaceable in the world-renowned pallets. Newly, citrazine acid was also used as a passive component for the synthesis of dyes and its preparation is very simple and the colorants prepared in coloristic application have the same level as the inclusion of other pyridone derivatives. As the yellow component, for example, the preferred aminoazo dye, the active component of which is 1,3-phenylenediamine-4-sulfoacid and the passive component citrazine: 2250 35 2250 35 2, has been shown to be the preparation of the reactive green from the pyridine-2,6-dione derivatives.

C00H

Its synthesis of N-ecetyl-m-phenylenediamine sulfoacid acid, the copolymerization of the resultant citric acid and the desecetylization of the resulting amino-color is technologically undemanding, reactive yellow monochlortrlazine (as a non-colored component sulphanilic acid) and dichlorotriazine type exhibit favorable coloristic properties as well as economically. interesting for the manufacturer.

However, other suitable aromatic diamines or suitable heterocycles, preferably containing one or more polyolysis groups, e.g., -SO2H, -COOH, may be used as active components for coupling with citrezinic acid.

The condensation products of (1-amino-4-bromoanthrachinone-2-sulfo-acid): 1-amino-4- (3'-aminophenylamino) -antrachinone-1-amino-4- (3'-aminophenylamino) -antrachinone have proven to be the color components of the blue shade for the preparation of the reactive green. 2,4'-disulfocylene, 1-amino-4- (4'-aminophenylamino) -antrachlnone-2,3'-dlsulfoacid, 1-amino-4- (2 ', 4', 6 '-trimethyl-3' -emino-phenylamino) -antraquinone-2,5 '-di sulfo acid.

These blanks are commonly manufactured on a production scale as colored components of the re-active blue, and their extensive application is due to satisfying colorietic properties of the drugs of the structure, which are also beneficial in the synthesis of mono-chlorotriazine-type greens.

According to the present invention, the reactive green of the formula I

Cl and An (I) NH-B,

wherein B 1 is a group of formula II

wherein R is hydrogen or alkyl of 1 to 4 carbon atoms and B2 is of formula III

COOH

wherein Ar is a C 6-10 aryl or a 5-6 membered heteroaryl group containing from 1 to 3 heteroatoms selected from nitrogen, sulfur and oxygen, preferably containing at least one solubilizing group, to prepare to condense in aqueous 2250 35

medium at 0 to 10 ° C cyanuric chloride with color component B, -NH 2, where E 1 is as defined above, and the resulting condensation product of formula IV

Cl

N ^ N NH-B, (IV)

is allowed to react at a temperature above 20 ° C with the color component 32-N 1 2, as defined above. The color components of the yellow shade (B2-NH2) can advantageously be used in the structure of formula V

COOH

= N

The SO3H HO 'N' OH (7) and the color components of the blue shade (Bj-NH2) can be advantageously recommended by the inventively produced 1-amino-4- (aminosulfophenylamino) -2-antrechinone sulfonic acid base. Indeed, the actual synthesis of reactive greens of this structure utilizes past experience to produce monochlortriazine reactive borvores. It is technologically and non-annually non-annual and can be carried out under normal operating conditions in operating conditions. In many laboratory experiments, it has been found to be preferable to carry out, in a known manner, cyanurocidivatives of bromamic acid (blue component) and obtain the dichlorotriazine berviva blue blue condensation with aminoazoberviver citrosine (yellow component). The post-synthesis isolation is viable with the usual methods used in technologically active dyes, and it is not necessary to use technological procedures unusual in the production of synthetic dyes for drying the pastes obtained.

The following examples illustrate the preparation of the reactive greens according to the present invention. EXAMPLE 1 222.4 g of 1% amino-4- (3'-aminophenylamino) anthracinone-2,4 ' -disulfoacetic acid paste (48.95 g of 100% substance = 0.1 mol) is stirred in 500 ml of water. ) to a homogeneous suspension, the volume is adjusted to 700 ml (concentration about 70 g / l) and allowed to stir overnight after heating to 35 ° C. Adjust the pH of the suspension to 5 to 6 with c (HCl) = 2.5 mol / l PH of the suspension on the second day with stirring, add 1 g of Spolion 8 and load in 20 min with external ice cooling at 5 ° C 19.4 g of cyanuric chloride (105% of theory).

After loading, the pH is adjusted to 5 to 6 with a soda solution of £ (| Ne 2 CO 3) = 2.5 mol / l, and the reaction mixture is stirred under stirring at pH 3 to 5 ° C. until disappearance of the starting material from the reaction mixture (chromatographic control).

After cyanuration is complete, 37.2 g of 100% 2,6-dihydroxypyridine-3-C3-amino-6'-sulfo-phenylazo) -4-carboxylic acid is added in the form of a clear neutral aqueous solution of 0.1 mol / l, prepared by by dissolving the paste of the substance in water with a solution of sodium hydroxide at a concentration of c (NaOH) = 2.5 mol / l followed by cleavage. The reaction mixture is briefly shaken, with a constant pH of 5 to 6 using a soda solution of c (j Na 2 CO 3) = 2.5 mol / 225035 4 and heated to 60 ° C and kept constant at this temperature. the volume of the liquid is long after it is complete by chromatographic control of condensation.

The reaction mixture is freed from cleavage of insoluble matter after condensation is complete at 60 DEG C., the dye is salted out of a solution of about 1800 ml with 450 g of NaCl (25% w / v) and the resulting suspension is stirred at room temperature. The solid is sucked off sharply and the paste of the dye is dried in the form of an aqueous suspension in a stream of hot gases, not spray-dried. 160 g of sieve is obtained seminally, which stains cellulosic materials in unusually rich green shades. It is a reactive dye of the following structural formula:

Example 2

400 ml of a finely divided suspension stirred at 24.5 g of 10096 1-amino-4- (1-amino-4- (1-amino-4-) (100.5 g) was added evenly to the prepared suspension of 9.45 g of cyanuric chloride (0.05125 mol) in 200 g of ice and 50 g of water. 4 ' -aminophenylamino) -antraquinone-2,3 ' -disulfoacid (0.05 mol) in water, to which 8.2 ml of c (Nb2CO3) soda solution = 2.5 mol / l was added prior to dosing.

Thereafter, the reaction mixture is stirred for a long time until the chromatography is complete by chromatography. The temperature is still maintained at 5 ° C by adding 150 g of ice to the reaction mixture as well as external cooling if necessary. During cyanuration, the pH value does not fall below 4, otherwise the soda solution of Nag (Nag NagCO ^) = 2.5 mol / l is dosed. At the same time, dissolving 62 g of 30% 2,6-dlhydroxypyridine-3- (3-emino-6'-sulfophenyl-azo) -4-carboxylic acid paste (18.6 g of 100% substance, i.e. 0.0525 mol) in approx. 400 ml of water and approx. 50 ml of sodium hydroxide solution (NaOH) = 2.5 mol / l prepare a solution of 0.1 mol / l concentration and pH = 7, 0.5, overfill and, after the cyanuric acid has ceased, adheres to the reaction mixture. Condensation is carried out in the same manner as in Example 1.

After completion of the condensation, insoluble fractions were removed from the reaction mixture by cleavage at 60 ° C. 337.5 g of NaCl (25% w / v) are metered into a clear solution of about 1350 ml of dye at 60 ° C, the suspension is stirred at room temperature and then sharply aspirated on a Bichr funnel. The cake obtained is finely dispersed in water and dried on a spray drier. 75 g of a green reactive dye solid of the following structural formula are obtained: 5 225035

Monochlortriazine reactive dye of structural formula

with the same procedure as in Example 1. Cyanureate of 1-amino-4- (2,4,4z, 6z-trimethyl-3Z-aminophenylamino) anthraquinone-2,5'-disulfoacid is carried out in a manner which is condensed. with 2,6-dihydroxypyridine-3- (3-amino-6Z-sulfophenylazo) -4-carboxylic acid as well as the following dye isolation as in the example. Example 4

When an equivalent amount (0.105 mol) of 2,6-di-hydroxypyridine-3- is used in place of 2,6-dihydroxypyridin-3- (3Z-amino-6Z-8-sulfophenylazo) -4-carboxylic acid in the dye synthesis of Example 1 (3'-amino-2 ', 4', 6'-trimethyl-5'-sulfophenylazo) -4-carboxylic acid, a green monochlorotriazine reactive dye of the following structural formula is obtained:

Claims (4)

Example 5 In the same manner as in Example 1, 1-amino-4- (3'-amino-phenylara) -8-tetraquinone-2,4-disulfoacid is condensed with cyanuric chloride, followed by the addition of a solution of 2.6- dihydroxypyridine-3- (4'-amino-3 '- sulfophenylezo) -4-carboxylic acid, containing 0.105 mol100% of the substance, and condensation, isolating the dye 1 by drying is carried out analogously to Example 1. A reactive green is obtained , whose main component is the substance of the following structural formula: COOH Said reactive bervins are dark green powders, in which, in addition to the basic substances of said structural formulas, accompanying organic impurities and inorganic salts are present. They dissolve very well in water to green solutions, the difference in color of which is not dependent on the solute. Due to their structure, all the substances described are capable of forming a chemical bond with some textile materials and can be used to form green shades by both coloring and printing. Coloristic application can be accomplished by all conventional techniques used for reactive dyes with a triazine structure in the molecule, and, for example, when applying the dyes described herein to cellulosic materials, rich green dyes with high wet fastnesses and very good light fastnesses are not present in any reactive palette. dyes. P S E D M ULE OF THE INVENTION 1. Reactive green of formula I B, -NH C1 N2 N N A, N NH Bn (I) wherein the group of formula II is Wherein R is hydrogen or alkyl of 1 to 4 carbon atoms and B2 is of formula III COOH wherein Ar is 6 to 10 carbon atoms or a 5- to 6-membered heterocycle radical and 1-3 heteroatoms from nitrogen, sulfur and oxygen, preferably containing at least one solubilizing group. 2. A process for the preparation of reactive greens of the general formula (I), characterized in that the cyanuric chloride with the color component B @ 1 -NH @ 2, as defined above, is condensed in an aqueous medium at 0 to 10 DEG C. and the resulting condensation product of the formula (IV) Cl is allowed to react at a temperature above 20 ° C with the color component B2-KH 2, where B2 is as defined above. 3. Process according to claim 2, characterized in that the color component B2-NH2 is preferably an amino-azo dye of the structural formula V COOH. 4. Process according to claim 2, characterized in that industrially produced intermediates are used for the base of bisquinone sulfonic acids. 1-amino-4- (aminosulfophenylamino) -2-anthra-