JPS59108769A - Preparation of 3-hydroxyquinophthalone derivative - Google Patents

Abstract

PURPOSE:To prepare the titled compound in high purity, economically, by condensing 3-hydroxy-2-methylcinchonic acid with trimellitic anhydride using tetramethylene sulfone as a reaction solvent, and esterifying the reaction product without separating from the reaction mixture. CONSTITUTION:3-Hydroxy-2-methylcinchonic acid is condensed with trimellitic anhydride in the presence of tetramethylene sulfone to obtain 3-hydroxyquinophthalone compound of formula I . Without separating the product from the reaction mixture, the carboxyl group of the product is esterified to methoxyethoxycarbonyl group or ethoxyethoxycarbonyl group in the presence of the above solvent. The objective compound of formula II (R is CH3 or C2H5) having sufficiently high purity to be used as a resin colorant without purification can be prepared by this process extremely economically in an industrial scale, without causing water pollution.

Description

Detailed Description of the Invention The present invention uses tetramethylene sulfone as a reaction solvent.
The present invention relates to a method for producing hydroxyquinophthalone derivatives.

More specifically, 3-hydroxy-2-methyl cinchoninic acid and 1-limellitic anhydride were subjected to a condensation reaction in the presence of tetramethylene sulfone, and the resulting formula (II)
, Without separating the first 3-hydroxyquinophthalone compound represented by formula (II), the carboxyl group of the compound of formula (II) is esterified to a methoxyethoxycarbonyl group or an ethoxyethoxycarbonyl group (5, formula (1) [Formula First 3-hydroxyquinophthalone represented by (■), R is methyl or ethyl group 1. Method for producing an outer conductor.

In the present invention, the 3-hydroxyquinocron derivative Δ represented by formula (I) can be used for dyeing various fibers such as nylon, polyester, cellulose acetate, polyolefin, polyurethane, etc., and polystyrene (PS).
Coloring of polyolefin resins, polyvinyl chloride 4ff+ fats, polyamide 1-resins, etc. It is a well-known soup that is extremely useful.

These compounds are generally prepared by carrying out an acid condensation reaction with 3-hydroxy-2-methylquinoline or 3-hydroxy-2-methylcinchoninic acid and 1-limeric anhydride 1 to obtain the above formula (Jl). First, the condensation reaction product of the compound is isolated and esterified with cellosolves or P-1 to luenesulfonic acid alkoxyedyl esters to obtain a compound of formula (I) which responds to the audible response.

In the condensation reaction, the anhydride of 3-hydroxy-2-methyl cinchoninic acid and O-dicarboxylic acid is reacted with phthalic anhydride, 0-dichlorobenzene, 1-dichlorobenzene and 21-dicarboxylic acid. A condensation method using various inert solvents such as U.S. Pat.
No. 23213 and No. 3023214,21 but in these 11 methods, lumps occur during and after the condensation reaction, making it difficult to stir, and the condensation reaction lumps are separated into threads,
However, it was difficult to further react the condensation reaction product as it was, so 3-hydroxy-2-methyl cinchonisiic acid was extracted. and arylpolycarboxylic anhydride, 1+11
For example, a method in which N-alkylpyrrolidone is used as a solvent during the condensation reaction during condensation with 1-limeric anhydride or phthalic anhydride, and after the reaction is completed, the reactant is treated with a lower alcohol and separated is also disclosed in Japanese Patent Application. 11 disclosed in 1972-56722. Although this method can alleviate the difficulty of stirring during the engineering condensation reaction, it has the disadvantage that the reaction during the condensation reaction is slow and the yield is low even if the reaction is carried out for a long time.

In this way, in order to carry out the first condensation reaction of the compound of formula (1) and further esterification reaction of the compound of formula (11) to the compound of formula (I) by a known method, the compound of formula (1) must be separated. After the reaction to the compound of formula (I) was first carried out using a selectively inert solvent.

The present invention provides an industrially very advantageous method for producing a highly pure 3-hydroxyquinophthalone derivative represented by formula (I), and includes a condensation reaction of a 3-hydroxyquinophthalone compound represented by formula (11). The compound of formula (I) is subsequently produced using the same solvent used in producing the product.

Next, embodiments of the method of the present invention will be described. 3- in the presence of tetraheramylene sulfone as a solvent during the condensation reaction.
For 1 mole of his-1-roxy-2-methyl cinchoninic acid,
Trimerisol l-acid anhydride is used in a molar ratio of 0.5 to 3, and the solvent te-1-ramethylene sulfone (3-hydroxy-2-methyl cinchoninic acid) is used in an amount of 4 to 10 mol per 1 mol.Additionally, nitrobenzene and trichloro are used as necessary. In the condensation reaction of the present invention, an inert solvent such as benzene, 0-dichlorobenzene, 0-21-hellotoluene, chlornaphthalene, and te-1-lahydronaphthalene may be added to 11 during or after the condensation reaction. When the starting materials are put into a mixing device (a) and a reactor (a) and are condensed at a temperature of 21.175-22 (1'Q), the reaction is completed in 1-12 hours.

Condensation reaction (very preferred temperature (1200-205
At C, the water produced in L6 is continuously distilled out of the reaction system from a cooler and separated.

After the completion of the condensation reaction, the temperature of the first reaction solution was 80-150'C.
Then, to obtain the compound of formula (1), the compound of formula (11
) Esterification of methyl cellosolve and ethyl cellosolve is carried out via desalting reaction of the compound or acid chloridation.

Esterification by desalting reaction is carried out by cooling the condensation reaction solution of the compound of formula (1) to Y100-150'c, adding an alkaline solution such as potassium carbonate or soda ash, and converting it to potassium or sodium salt of carboxylic acid. -Add 10 to 20 molar ratio of P-toluenesulfonic acid methyl-1-xyethyl ester or P-1-toluenesulfonic acid methoxyethyl ester to hydroxy-2-methyl cinchoninic acid,
Keep warm at 0-150'Q for 2-10 hours and esterify? Terminate it.

In order to perform esterification via acid chloride (2, 201), the condensation reaction liquid of the compound was cooled to 80-120'C, and 1
Addition of acid chloride such as subnyl chloride and phosphorus oxychloride in a molar ratio of 0 to 20 is carried out at the same temperature for 1 to 5 hours to complete the acid chloride reaction. At this time, addition of a small amount of dimethylboramide σ) is effective in promoting the reaction. To this reaction solution, 1.0 to 30 molar ratio of methyl cellosolve or (
Add ethyl cellosolve, 1 to 5 at 1oo to 130'Q.
Keep warm for an hour to complete esterification.

In either case, after the esterification reaction is completed, metamer or Q-based water is added, and the precipitated crystals are filtered, washed with water, and dried to obtain a high-purity quinophthalene compound represented by the formula (f).
The jt isomer is obtained in a low yield.

After separating the first compound of formula (I) thus obtained,
The recovery of Alco-1 and Teramedilence I from single-use liquids is mostly produced without discharging waste liquids to the outside, so there is no problem of water pollution. In addition, the compound of formula (1) obtained by the method of the present invention,
Since it can be obtained in cylinder purity, there is no need for any purification, and 2't used as a resin coloring material has an extremely high fI+
Can be colored in 1 light.

Examples are shown below.

[Example 1] Add 21.1' of anhydrous trimeryic acid and 90 gk of tetramethylene sulfone to a reactor, and add +9Q while stirring.
Dissolved by heating at ~200"C., 3-hyroxy2
-Medyl cinchoninic acid 2039 and 19Q to 200-Q were charged for 1 hour, and then mixed at 200'Q for 3 hours. During that time, water generated during external temperature and heat retention was distilled out of the reaction system through a cooler and separated. After the condensation reaction was completed, the solution was cooled to 100'0, but no solidity was observed at all. 1c Trichlorhenzene 659 t
7JI]λ, dimethylborumami)-o, 3 gY was added as a catalyst, and thionyl chloride 31so was added at 90'c, followed by stirring at 125-13Q'c for 3 hours to carry out an acid chloridation reaction. 16.6°C of methyl cellosolve was added, and after stirring at 25'O for 2 hours, it was cooled to 80'Q and discharged into 200°C of methanol. After cooling to 25°C, the mixture was filtered, washed with methanol at 100°C, washed with water, and dried to obtain 301 g of a bright yellow powder. [Yield near 6
．． 8% vs. 3-hydroxy-2-medyl cinchonine iW)
.

The dye IX has the following structural formula and dyes acetate-1-fibers and polyester fibers to a reddish yellow color.

[Example 2] The reaction solution obtained in the same manner as in Example 1 after completion of the condensation reaction was cooled to 120'C, 14 g of potassium carbonate was added, and p-toluenesulfonic acid was added. Add methoxyethyl ester 2G, OE'' and stir at 120'Q for 2 hours. After reaction, cool to room temperature, 80% methanol 2
009 Y, C was added to λ, filtered, washed with water, and dried to obtain 33 g of a dye having the same structural formula as that obtained in Example 1.

This material (method, similar to the dye of Example 1, acetate, , 1
-(J! Fibers and polyester fibers were vividly dyed in reddish yellow.

patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims]] 3-hy-1-[]]x-2-methylcinchonine,
Trimeriso anhydride 1 to acid are subjected to a condensation reaction in the presence of tetramethylene sulfone, and then the carboxyl group of the compound of formula (II), methoxyethoxycarbonyl group or ethoxyethoxy, is obtained. Formula (I) characterized in that carbonyl group is esterified;
A method for producing a 3-hydroxyquinophthalone derivative.