CS206995B1 - Method of preparation of the antrachinon dyes with the triazine cycle - Google Patents

Description

( ⁵⁴ ) A method for preparing anthraquinone dyes and a triazine cycle

The invention relates to a process for the preparation of anthraquinone bervatives with a triazine cycle by reacting 1-chloro- or 1-bromoanthraquinones with benzoguanamine.

The preparation of anthraquinone dyes with a triazine cycle from benzoguanamine and 1-halogen nantraquinones was patented (Soviet Patents No. 120,625 and No. 130,596) and published by Soviet authors Titkov and Pletnev (Journal of Obscure Chimii 33, 1983 (1963)). The yields of insoluble dyes thus prepared are mostly below 80% of theory and the dyes contain an undesired semicondensate, which is the product of benzoguanamine substitution by anthraquinone residue on only one amino group.

A recent Cibn-Geigy patent (U.S. Pat. No. 3,839,332) protects the process by utilizing the solubility of the copper iodide-pyridine complex to catalyze the reaction, allowing dye yields above 90% of theory to be achieved at lower temperatures than required by the Soviet authors. The reaction is carried out in the presence of soda and requires a period of min. 12 hours, in which case the semi-condensate reacted completely in a larger batch and a part of the starting halogenantraquinone was hydrolyzed in parallel. It has now been found that if an acid-binding agent is used in place of soda ash of alkali, optionally crystalline bicarbonate or crystalline soda, the above-mentioned drawbacks of the process are eliminated.

A process for the preparation of anthraquinone triazine ring dyes of the formula I

y

/ 1 /

£.

208 99S where X represents a non-ionic substituent such as hydrogen, chlorine, methyl, benzoylamine, by reaction of 1-chloro- or 1-broraantraquinone of formula II,

(II) wherein X has the same meaning as in formula I, with 2-phenyl-4,6-diamino-1,3,5-triazine in an organic solvent in the presence of an acid binding agent and in the presence of cuprous iodide and pyridine, according to the invention in that the reaction is carried out in the presence of MeHCO 4, wherein Me is Na or K, NaHCO 4. 21? O and optionally NagCO ?. 10 HgO in an amount of 2 to 4 moles of MeHCO ₃ , NaHCO 3. 2 HgO _{or 1/2} , _{10 per mole of} haloanthracinone.

The advantage of the patented process is that at temperatures above 100 ° C hydrates, while distilling off the crystalline water, liberate alkaline in a very fine form, which is perfectly reactive, better than, for example, anhydrous soda as such, and thus obtainable product in quantitative yield over 1/2 to 1/3 reaction time than soda. The use of said bicarbonates makes it possible to preserve the copper in the monovalent form by virtue of the lower pH of the reaction mixture. Moreover, the dyes thus prepared are highly pure and do not contain any semi-condensate or by-products.

The preparation of the dyes according to the invention is preferably carried out in a nitrobenzene medium at temperatures of 130 to 175 ° C, preferably at 150 to 160 ° C, and in the presence of a catalyst which is a copper (I) iodide-pyridine complex. The catalyst may be added to the reaction mixture either as cuprous iodide and in particular pyridine, as a solution of both components in an organic solvent, preferably nitrobenzene, or may be prepared from copper, iodine and pyridine in situ. The molar ratio of catalyst to 1-chloro- or 1-broraantraquinone entering the reaction may be 0.01 to 0.1, usually 0.02 to 0.05 mol / mol. When an amyl alcohol or other aliphatic alcohol having 4 to 6 carbon atoms is used as solvent, the reaction is carried out under pressure in an autoclave.

As 1-chloro- or 1-bromoanthraquinone of formula II, they may be used

- chloantraquinone

1,5 - dichloranthraquinone

1,8-dichloroanthraquinone

- chloro - 2 - methylanthraquinone

- bromo - 4 - methylaminoantraquinone

- chloro - 4 - benzoylaminoantraquinone

- chloro - 5 - benzoylaminoantraquinone

- chloro - 8 - benzoylaminoantraquinone, the examples given are not exhaustive of the reaction of the useful compounds.

The dyes obtained are useful as pigments for dyeing polymers and synthetic fibers, in paints and baking varnishes or as vat dyes and include yellow, orange, red, violet, brown or blue shades.

Examples

Example 1

8.4 g of benzoguanamine, 23 g of 99.8% 1-chloroanthraquinone, 27 g of crystalline sodium bicarbonate, 0.6 g of iodine, 0.45 g of copper powder and 6 g of pyridine are stirred in 100 g of nitrobenzene. with stirring, heated to 155 ° C, leaving about 10 ml of distillate through a descending condenser, and stirred at 150-155 ° C for 5 hours. The reaction mixture is diluted with 50 g of nitrobenzene, heated to 150 ° C, the product is filtered off with suction and washed with hot nitrobenzene until the effluent filtrates are colorless. Then 50 g of ethanol are washed and the paste is freed from the solvents by distillation with steam.

206 995

The alkaline aqueous suspension of the product was oxidized at 90-94 ° C with sodium hypochlorite solution, suction filtered while hot and washed with 200 ml of water. The resulting paste is stirred in 300 ml of water acidified with 15 ml of 2.5 N hydrochloric acid, heated to 90-94 ° C for 30 minutes, filtered off and washed with water until the filtrate flows neutral. The product paste contains 26.7 g (99%) of yellow dye I (X = H).

Example 2

22.5 g of benzoguanamine, 64.7 g of 1-chloroanthraquinone are mixed in 400 g of nitrobenzene.

94.5%, 52 g freshly dried sodium bicarbonate, 0.8 g iodine, 0.4 g powdered copper and 9 g pyridine, heated at 155 ° C for 6 hours, diluted with 100 g nitrobenzene and the product sucks off. Further work-up is similar to Example 1, yielding 67.6 g of yellow pigment (93.9 theory).

Example 3

A suspension of 5.6 g of benzoguanamine, 16.2 g of 1-chloroanthraquinone 94.5%, 22 g of crystalline soda, 0.6 g of copper iodide and 4 g of pyridine in 100 g of nitrobenzene is heated to 150-160 ° with stirring for 6 hours. C. The reaction mixture was diluted with 25 g of nitrobenzene, filtered while hot and the paste was washed with hot hitrobenzene and ethanol. Further work-up is analogous to Example 1. Yield: 17.1 g (95% of theory) of a yellow pigment.

If, in Examples 1 to 3, a corresponding amount of substituted 1-chloro- or 1-bromoanthraquinone is used instead of 1-chloroanthraquinone, the dyes of the formula I are obtained in good yields, the shades of which are given in the table.

TABLE

Color shades from the reaction of benzoguanamine with substituted 1 - chloro - or 1 - bromoanthraquinones

Default anthraquinone Hue

- chlorantraquinone

- chloro - 2 - methylanthraquinone

1,5 - dichloranthraquinone

1,8-dichloroanthraquinone

- bromo - 4 - methylaminoantraquinone

- chloro - 4 - benzoylaminoantraquinone

- chloro - 5 - benzoylaminonantraquinone

- chloro - 8 - benzoylaminoantraquinone yellow orange yellowish brown reddish brown blue red orange orange

Example 4

The autoclave was charged with 16.8 g of benzoguanamine, 46 g of 1 - chloroanthraquinone containing

99.8%, 32 g of freshly dried sodium bicarbonate, 1 g of iodine, 0.5 g of copper powder, 15 g of pyridine and 200 g of nitrobenzene, after closing, the mixture is stirred and heated to 160 ° 0, which is then held for 24 hours . After cooling, the product is isolated and the solvent is removed by hot extraction to remove residual unreacted semicondensate. The yield of 40 g is 74% of the yellow pigment theory.

Claims (1)

SUBJECT Feces from U A process for the preparation of anthraquinone dyes having a triazine ring of formula (I): (X) wherein X is a non-ionic substituent such as hydrogen, chloro, methyl, benzoylamino, by reaction of 1-chloro- or 1-bromoanthraquinone of formula (II) with the same meaning as in formula I, with 2-phenyl-4,6-diamino-1,3,5-triazine in an organic solvent in the presence of an acid binding agent and in the presence of cuprous iodide and pyridine, characterized in that the reaction is carried out under presence of IvleHCO3 Wherein Me is Na or K, NAHCO3. 2 HgO or NagCO 3 - 10 HgO in an amount of 2 to 4 moles of MeHCO 4, NaHGO 4 · 2 HgO or 1/2 NagGO 4 · 10 HgO per 1 mole of halanthraquinone ·