JPS597736B2 - Method for producing quinophthalone compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 3-
The present invention relates to a method for producing a hydroxyquinophthalone compound.

More specifically, 3-hydroxy-2-methyl cinchoninic acid and formula (■).

Te゜□. Phenyldicarboxylic anhydride, tetramethylene, represented by C(■) (wherein Z is hydrogen, a halogen atom, or a -COOH group, Y is a halogen atom, and m is o or an integer from 1 to 3) By reacting in the presence of sulfone, formula (I), □
CH<? □m 11 (In formula (I), Z, Y, and m are the same as in formula (■) above.

), it relates to a method for producing a 3-hydroxyquinophthalone compound. 3-Hydroxyquinophthalone compounds are used for dyeing various fibers such as nylon, polyester, cellulose acetate, polyolefin, polyurethane, etc., as well as polystyrene (PS resin), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene. It is an extremely useful compound for coloring copolymers (ABS resins), polyolefin resins, polyvinyl chloride resins, polyamide resins, etc.

These compounds are generally produced by condensing the corresponding 2-methylquinoline derivative with an arylpolycarboxylic acid or its anhydride, but known methods have problems in product separation and quality, making industrial production methods difficult. It cannot be said that it is appropriate.

For example, U.S. Patent No. 2006022 discloses the production of 3-hydroxyquinophthalone by condensing 3-hydroxy-2methylquinoline and phthalic anhydride, but in this method, the condensation reaction occurs in a molten state; After the reaction is completed, when discharging into water, the molten reactants form large lumps due to cooling, making it difficult to stir and discharging. The compound obtained by this method has poor dispersibility and loses commercial value, especially when coloring a PS resin that requires sharpness and transparency, because black impurities are difficult to dissolve in the resin. Therefore, purification using an organic solvent is necessary. Also, regarding this condensation reaction, with 3-hydroxy-2-methyl cinchoninic acid. - in the solvent used in the reaction with dicarboxylic acids and/or their anhydrides, such as phthalic anhydride. - Methods in which various inert solvents such as dichlorobenzene, trichlorobenzene, and nitrobenzene are used have also been proposed (U.S. Pat. Nos. 3,023,213 and 3,023,214); It has drawbacks in sharpness and transparency and requires purification. Furthermore, when condensing 3-hydroxy-2-methyl cinchoninic acid with an arylpolycarboxylic acid such as phthaldic anhydride or trimellitic anhydride, N-alkylpyrrolidone is used as a reaction solvent, and after the reaction is completed, the reaction product is treated with a lower alcohol. A method of separating it as a precipitate is disclosed in Japanese Patent Application Laid-open No. 48-567.
It is disclosed in 22. Although this method is characterized by overcoming or alleviating the difficulty in producing quinophthalone compounds and the quality deterioration associated therewith, it has the drawbacks of slow reaction and low yield even if the reaction is carried out for a long time. The present invention provides a highly advantageous industrial method for producing highly purified 3-hydroxyquinophthalonated compounds.

That is, the method of the present invention involves carrying out the condensation 4 reaction of the compound of formula () with 3-hydroxy-2-methyl cinchoninic acid in the presence of tetramethylene sulfone as a solvent during the reaction.

Condensation is carried out at a reaction temperature of 175 to 220°C, and after the completion of the reaction, the reaction mixture is cooled to 80 to 120°C while stirring to precipitate crystals, and if desired, lower alkyl alcohol (hereinafter referred to as alcohol) is added to form a reaction mixture. By diluting it, filtering it, washing it with alcohol, and drying it, a quinophthalone compound of extremely high purity and quality can be obtained in high yield.

According to the method of the present invention, when producing other derivative colorants by further reacting the reaction product 3-hydroxyquinophthalone compound represented by formula (), it is possible to add the reaction product to the condensation reaction mixture without isolating the product. Subsequently, various reactions can be carried out. In the method of the present invention, 3-hydroxy-2
- The compounds represented by the formula () to be reacted with methyl cinchoninic acid are phthalic acid, trimellitic acid, 3-chlorophthalic acid, 4-chlorophthalic acid, 3,5-dichlorophthalic acid, 3
Examples include anhydrides of -bromphthalic acid, 3-fluorophthalic acid, 4-fluorophthalic acid, and tetrachlorophthalic acid.

Next, embodiments of the method of the present invention will be described.

These anhydrides are used in a molar ratio of 0.5 to 3 per mole of 3-hydroxy-2-methyl cinchoninic acid in the presence of tetramethylene sulfone as a solvent during the reaction, and the solvent tetramethylene sulfone is It is desirable to use 4 to 10 moles per mole of -2-methyl cinchoninic acid.

The starting material was placed in a reactor equipped with a stirring device and heated to 175~
When the condensation is carried out at a temperature of 220°C, the reaction is completed in 1 to 12 hours.

A very preferred temperature for the reaction is 200 to 205°C, and water produced during the reaction is distilled out of the reaction system through a cooler and separated.

After the reaction is completed, the resulting mixture is cooled to 80 to 120°C to precipitate crystals, and methyl alcohol, ethyl alcohol,
The reaction product is diluted by adding isopropyl alcohol or a mixture thereof, filtered, washed with alcohol, and dried to obtain a highly pure 3-hydroxyquinophthalone compound. Next, Examples will be shown to further specifically explain the method of the present invention.

Example 1 3-hydroxy-2-methyl cinchoninic acid 15 was added to the reactor.
9. Add phthalic anhydride 221 and tetramethylene sulfone 45f1, gradually raise the temperature to 200-205°C,
It was kept at that temperature for 6 hours.

The water generated during heating and keeping the temperature was distilled out of the reaction system from the cooler and separated. Next, the mixture was cooled to 120°C, 50ml of methyl alcohol was added and stirred at 65-7°C to form a suspension, cooled to room temperature, filtered, washed with methyl alcohol until the washings became clear, and dried. , 17.59 (yield 82(f) vs. 3-hydroxy-2-methyl cinchoninic acid) of a bright yellow powder was obtained. This dyed PS resin in a transparent bright yellow color, and also dyed acetate fibers and polyester fibers in a bright yellow color. This dye had the structure of the following formula. In addition, N instead of tetramethylene sulfone
- When the reaction was carried out in exactly the same manner except for using methyl-2-pyrrolidone, the yield of the target product was as low as 580 t).
The clarity when colored with the S resin was also somewhat inferior to that obtained in Example 1.

Also in place of tetramethylene sulfone. - When dichlorobenzene was used, the reactant formed into a large lump after the reaction was completed, making stirring difficult. Example 2 21.19 g of trimellitic anhydride and 90 g of tetramethylene sulfone were placed in a reactor, and while stirring,
The mixture was heated and dissolved at 200°C.

After charging 20.3 g of 3-hydroxy-2-methyl cinchoninic acid at 190 to 200° C. over 1 hour, the mixture was stirred at 200 g C for 3 hours.

The water generated during heating and keeping the temperature was distilled out of the reaction system from the cooler and separated. After the condensation reaction was completed, it was cooled to 100°C and 200f of methanol was added. It was discharged inside. After cooling to 25° C., it was filtered, washed with 100 g of methanol, washed with water, and dried.

Yield: 31.390 (Yield; 94.00 I) vs. 3-hydroxy-2-methyl cinchoninic acid).

This dye had the following structural formula. Example 3 Dissolve 8.69 g of 3-hydroxy-2-methyl cinchoninic acid in 100 g of tetramethylene sulfone and, stirring the solution constantly, dissolve 17.59 g of tetrachlorophthalic anhydride.
was added gradually.

The reaction mixture was heated at 200° C. for 10 hours, then cooled to 900° C. The reactant was discharged into 4009 water, and the precipitated crystals were filtered, washed with water, and then dried to obtain the following compound. 0C
1 When used in polyprolene resin, this pigment colored yellow with excellent light resistance, solvent resistance, and heat resistance.

Claims (1)

[Claims] 1 3-hydroxy-2-methyl cinchoninic acid and the following formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) [In formula (II), Z is hydrogen or a halogen atom , or -COO
H group, Y is a halogen atom, m is 0, or 1 to 3
phenyldicarboxylic acid anhydride,
There are formula (I)▲mathematical formulas, chemical formulas, tables, etc.▼(I) [In formula (I), Z is hydrogen, a halogen atom, or a -COOH group, which is characterized by reacting in the presence of tetramethylene sulfone. , Y is a halogen atom, m is 0,
or an integer from 1 to 3].