CS263950B1 - Process for preparing 1,3,5-triazim compounds based on acetoacetic acid arylide - Google Patents

Abstract

Compounds of general formula I, in which R denotes SO3X, where X is sodium or potassium, are prepared by condensation of 2,4,6-trichloro-1,3,5-triazine with acetacet-2-anisidide in an aqueous medium or an organic solvent medium in the presence of sodium or potassium hydroxide. The reaction in an aqueous medium is carried out in the presence of surfactants. The condensation product is further dissolved in concentrated sulfuric acid, poured into ice-water and salted out with sodium or potassium chloride. The prepared substances are intermediates for the preparation of organic dyes.

Description

The present invention relates to a process for the preparation of 1,3,5-triazine compounds of formula (I)

in which

R is SO 3 X, wherein X is sodium or potassium.

German Patent Specifications 2,365,361 and 2,445,932, as well as Swiss Patent 574,944, disclose a preparation process by which the triazine compounds used in the preparation of dyes, in particular water-insoluble azo dyes, are obtained by a two-step synthesis consisting of: first in condensation of 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride) with acetoacetarylides, and then in hydrolysis to replace the remaining chlorines on the triazine ring with hydroxyls. At the same time, the acetyl present is cleaved and an active methylene group capable of reacting with diazonium salts to form azo dyes is formed.

The first stage of the synthesis of these patents is illustrated by an example from which it is apparent that the reactants, i.e., 396 parts of cyanuric chloride, 427 parts of acetoacet-2-chloroanilide and 80 parts of sodium hydroxide, are used practically in equimolecular ratio. Analogously, a triazine product derived from acetoacet-4-chloroanilide and some other unspecified derivatives are prepared in this ratio.

The substitution of chlorine on the triazine ring with hydroxyl and the hydrolytic cleavage of acetyl is carried out according to said patents by boiling in an acidic aqueous or alcoholic medium, or the dried condensate is dissolved in concentrated sulfuric acid and the solution is poured into ice.

A detailed study of the preparation of the triazine compounds of the aforementioned patents has revealed some drawbacks, particularly when acetoanilide and aeetoacet-2-anisidide were used for condensation. The problem was found to be insufficient alkalinity and thus incomplete reaction of condensation components, manifested in that the prepared substances contained unreacted strongly toxic cyanuric chloride. The presence of cyanuric chloride was further demonstrated by the fact that a considerable amount of 2,4,6-trihydroxy-1,3,5-triazine or cyanuric acid was found in the condensation product with acetoacetanilide. This is due to prolonged standing or heating of the reaction mixture, in which the initially neutral or weakly alkaline reaction becomes strongly acidic due to the hydrolytically cleaved hydrogen chloride.

It has found that these deficiencies having considerable economic and ecological impact can cdsirsnit appropriate modification of the known process, in particular by increasing the amount of hydroxide used in the condensation of cyanuric chloride with an acetoacetarylide and performing the isolation of the condensation product by heating the suspension after the condensation at 60 to 90 ^C C and acidifying or on the contrary, first by acidifying it and then by heating it.

Furthermore, it has been found that in the hydrolysis of the condensation product based on acetoacet-2-anisidide in concentrated sulfuric acid, in addition to the chlorine substitution of hydroxyls and the cleavage of acetyl, sulfonation is also formed to give the sulfoacid of formula I where R is a sulfo group. Due to the presence. active methylene groups, the sulfoacid of formula I can be used for the preparation of azo dyes capable of forming insoluble salts called lacquers.

A process for the preparation of 1,3,5-triazine compounds of formula I

wherein, R represents SO 3 X, wherein X is hydrogen or potassium, by condensing 2,4,6-trichloro-1,3,5-triazine with an acetoacetarylide of formula II

in aqueous medium using sodium or potassium hydroxide, optionally using an organic solvent such as acetone or dioxane and hydrolyzing the product obtained, according to the invention, consists in using cyanuric chloride, acetoacetarylide and sodium or potassium hydroxide in a molar ratio of 1: 1: 2a reactions in aqueous medium is carried out in the presence of surfactants such as condensates of ethylene oxide with higher fatty acids or alcohols, with a number of carbon atoms C ₁₈ through C _30th The resulting product is isolated after acidifying the suspension and heating to 60-90 ° C.

The condensation cyanuric chloride with acetoacetanisidide is dissolved in concentrated sulfuric acid, the solution is poured into ice water and the product is salted out with sodium or potassium chloride, filtered and washing with 10-15% sodium or potassium chloride solution to give a compound of formula I wherein R is SO₃X wherein X is sodium or potassium. The process according to the invention is illustrated by the following example wherein, unless otherwise stated, solids are parts by weight and liquid parts are parts by volume.

Example

19.63 parts of cyanuric chloride are dissolved in 150 parts of acetone or 50 parts of dioxane and the solution is added to a mixture of water and ice with stirring. A solution of 20.7 parts of acetoacet-2-anisidide in 100-150 parts of sodium hydroxide c (NaOH) = 2 mol / l is added to the suspension obtained under stirring at 0-5 ° C over 30-40 minutes.

After completion of the condensation, the suspension is acidified by the addition of hydrochloric acid, heated to 60-90 ° C, filtered off and washed with water. Melting point of the crude substance 160-165 ° C. It dissolves hot in benzene, adding petroleum ether or industrial gasoline to give crystals of m.p. 169-170 ° C. Product formula formulas

OCH,

CH 2 COCHCOHN

and (ni) was confirmed by mass spectroscopy and elemental analysis.

For C ₁₄ H ₁₂ Cl ₂ N ₄ O 3 (mol. Wt. 355.17) calculated:

% C, 47.34;% H, 3.41;% Cl, 19.96;% N, 15.77.

47.84% C, 3.76% H, 20.16% Cl, 15.60% N. The above example can be modified by carrying out the condensation with the exclusion of an organic solvent, i.e. in an aqueous medium with the addition of 3-5 % surfactant, for example, a condensation product of ethylene oxide with oleic acid, available under the trade name Slovasol A.

parts of the condensation product cyanuric chloride and acetoacet-2-anisidide are dissolved in 50 parts of concentrated sulfuric acid and the solution is stirred for 30 minutes, i.e. until the evolution of hydrogen chloride ceases and the liquid becomes clear. Now the hydrolysis mixture is poured into 100-150 parts of ice, the prodkut is salted out by adding 23-30 parts of powdered sodium chloride, vacuum filtered and washed on the filter with 15% NaCl solution. Purification from hot water yields a pure white sulfoacid sodium salt of formula

ChLCOHN

I i ’

HIM

OH (IV)

The constitution was confirmed by caustic alkaline cleavage to 2-aminoanisole-4-sulfoacid and by elemental analysis indicating that the substance contained crystalline water.

For C 14 H 17 N 4 NaO 5 S - (- H ₂ O (mol. Wt. 396.31) calculated:

% C, 36.36;% H, 3.30;% N, 14.16;

% C, 36.17;% H, 3.76;% N, 14.06;% Na, 5.75%.

For sodium, this is calculated from sulphated ash 17.75%.

Similarly, the potassium salt is prepared when potassium chloride is used instead of sodium chloride for salting out.

Claims (1)

Subject VYNALEZU A process for the preparation of 1,3,5-triazine compounds based on the acetic acid arylide of formula (I) wherein: R is SO ₃ X, where X is sodium or potassium, by condensing 2,4,6-trichloro-1,3,5-triazine with an acetoacetarylide of formula II and ₅ CH ₃ COCH ₂ COHN (II) in aqueous medium using sodium or potassium hydroxide, optionally using an organic solvent such as acetone or dioxane and hydrolyzing the product obtained, characterized in that the cyanuric chloride, acetoacetarylide and sodium or potassium hydroxide are used in a molar ratio 1: 1: 2 and the reaction in aqueous medium is carried out in the presence of surfactants such as condensates of ethylene oxide with higher fatty acids or alcohols having carbon number of C ₁₈ to C _30, the resulting condensation product of cyanuric chloride with acetoacetanisididem formula III after acidifying the suspension and isolated to 60-90 ° C, dissolved in concentrated sulfuric acid, poured into ice-water, and the product salted out with sodium or potassium chloride, filtered and washed with 10-15% sodium or potassium chloride solution.