CS263949B1 - A process for preparing a 1,3,5-triazine compound based on acetoacetic acid arylide - Google Patents

Abstract

The compound of formula I is prepared by condensation of 2,4,6-trichloro-1,3,5-triazine with acetoacet-2-anisidide in an aqueous medium or in an organic solvent 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 dissolved in a mixture of ethanol — concentrated sulfuric acid and the solution is poured into ice-water. The prepared substance is an intermediate for the preparation of organic dyes.

Description

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

OGH ₃

This can be eliminated by appropriate treatment of the known process, in particular by increasing the amount of hydroxide used in the condensation of cyanuric chloride with acetoacetarylides and further treating the condensation product by heating the condensation slurry to 60 to 90 ° C and acidifying or firstly acidifying it and then heating.

A process for preparing a 1,3,5-triazine compound of formula I

German Patent Specifications 2,365,361 and 2,445,932 and Swiss Patent 574,944 disclose a process by which triazine compounds used in the preparation of valuable dyes, in particular water-insoluble azo dyes, are obtained by a two-stage synthesis consisting first of condensation 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 phase of the synthesis of said patents is demonstrated by an example from which it is apparent that the reactants, 1j. 396 parts of cyanuric chloride, 427 parts of acetoacet-2-chloroanilide and 80 parts of sodium hydroxide are used in practically equimolecular ratio. The triazine product derived from acetoacet-4-chloroanilide and some other unspecified derivatives are prepared analogously 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 acetoacet-2-anisidide was 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 now been found that said nedostatCH.CONH] ¹

N

by condensing 2,4,6-trichloro-1,3,5-triazine with the acetoacetarylide of formula II

OCH., '\ _ - ^J // \\

CH, COCH, COHN ...... y ..... y (II) in aqueous medium using sodium or potassium hydroxide, optionally using an organic solvent such as acetone or dioxane, and thus hydrolyzing the product obtained According to the invention, in that the cyanuric chloride, acetoacetarylide and sodium or potassium hydroxide are used in a 1: 1: 2 molar ratio, the reaction in aqueous medium is carried out in the presence of surfactants such as ethylene oxide condensates with higher fatty acids or alcohols having carbon numbers _J2 to C ₃₀ . The resulting product is isolated after acidification of the suspension and heating to 60-90 ° C, then dissolved in a 1: 1 v / v ethanol / concentrated sulfuric acid mixture and poured into ice-water. The triazino derivative of the formula I obtained is characterized by the ability to coupling with diazo compounds. Thus, for example, with diazotized aminodimethyl terephthalate, pure color-rich yellow of very good fastness in organic solvents and high fastness to light is obtained.

The following example illustrates an improved process for the preparation of the 1,3,5-triazine compound of formula I. Unless otherwise stated, solids are parts by volume, the temperature being given in ° C.

Example.

19.63 parts of 2,4,6-trichloro-1,3,5-triazine 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 the condensation is complete, the suspension is acidified by the addition of hydrochloric acid, heated to 60-90 ° C, filtered and washed with water. The melting point of the crude substance is 160 to 165 degrees Celsius. It dissolves hot in benzene, adding petroleum ether or industrial gasoline to give crystals of mp 169-170 ° C. The composition of the product of the formula, for example, the condensation of ethylene oxide with high molecular weight fatty acids or alcohols having a carbon number of C | ₂ to C; _{! ()} . For example, ethylene oxide-oleic acid condensate available under the trade name Slovasol A is preferred.

The condensation product is further dehalogenated and de-acetylated by dissolution in a 1: 1 v / v mixture of ethanol and concentrated sulfuric acid. water, ethanol and petroleum ether. The yield of the derivative of the following formula is 85 to 90% th.

OCH, and ₃

CH 2 COCHCOHN and ^N cv were confirmed by mass spectroscopy and elemental analysis.

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

47.34% C, 3.41 θ / ο H, 19.96% Cl, 15.77% N, found:

% C, 47.84;% H, 3.76;% Cl, 20.16;

The condensation process can be modified by carrying out the reaction with the exclusion of an organic solvent, i.e. in an aqueous medium and with the addition of 3-5% surfactant CH ₂ CONH

HIM

The composition was confirmed by molecular spectroscopy and elemental analysis.

For C ₁₂ H ₁₂ N ₄ O ₄ (mol% 276.244) calculated:

% C, 52.17;% H, 4.38;% N, 20.28;

52.47% C, 4.79% H, 20.01% N.

With diazontic compounds, for example diazotized 2-aminoterephthalic acid dimethyl ester, it coupled to a colouristically very rich yellow pigment of high fastness to light and organic solvents.

Subject

Claims (2)

A process for the preparation of a 1,3,5-triazine compound based on the acetic acid arylide of formula I OCH: (I) by condensation of 2,4,6-trichloro-1,3,5-triazine with an acetoacetarylide of formula II ch ₃ cochocohne 7 (II) in aqueous medium using sodium or potassium hydroxide, optionally using an organic solvent , such as acetone or dioxane, and by hydrolyzing the product obtained, characterized in that cyanuric chloride, acetoacetarylide and sodium or potassium hydroxide are used in a molar ratio of 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 Article alcohols having carbon number of C ₁₂ to C _30, the resulting product, after acidifying the suspension and heating to 60-90 ° C is isolated. then it is dissolved in a 1: 1 v / v ethanol / concentrated sulfuric acid mixture and poured into ice-water. Severography, n. P., Plant 7, Most. Price 2,40 KCs