JPS59128373A - Preparation of quinophthalone compound - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as an intermediate of yellow dye, in the form of high-purity crystal having large particle size and excellent filterability, in high yield, by adding a quinaldine derivative to trimellitic anhydride in hot organic solvent, thereby effecting the reaction of the reactants and the decarbonation reaction of the product at the same time. CONSTITUTION:Trimellitic anhydride is dissolved in an organic solvent such as trichlorobenzene, and the solution is heated at 180-240 deg.C, preferably 190-230 deg.C. The quinaldine derivative of formula I is added continuously or intermittently to the hot solution under normal pressure for 1-20hr to effect the decarbonation reaction, and at the same time to react the trimellitic anhydride batchwise, and the mixture is cooled to 70 deg.C after the reaction. The reaction product is diluted with an organic solvent having poor solvent power such as methanol, cooled to <=50 deg.C, and filtered to obtain the high purity crystal of the quinophthalone compound of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a quinophthalone compound represented by the following structural formula [ll].

The quinophthalone compound of general formula [11] is useful as an intermediate for yellow dyes. As a method for producing this quinophthalone compound, for example, a method of reacting a quinaldine derivative with trimellitic anhydride can be considered, but the quinaldine derivative that is normally produced industrially is represented by the following structural formula [1]. It is a compound substituted with a carboxyl group at the da position. Therefore, industrially, the forefoot general formula (
When producing the quinoflerone compound II), a quinaldine derivative of general formula C shown above is usually used as a raw material (see, for example, Japanese Patent Publication No. 17-2017).
. When this quinaldine derivative is heated to about 170°C, a decarboxylation reaction occurs, and the carboxyl group at the q position is removed. Therefore, when producing the quinophthalone compound of the general formula (II) from the quinaldine derivative of the general formula (1) and trimellitic anhydride in a batch process, in advance,
One possible method is to heat-treat the quinaldine derivative to cause a decarboxylation reaction, and then add trimellitic anhydride to cause the reaction. In addition, since the reaction with trimellitic anhydride does not occur unless the temperature is higher than the temperature of the above-mentioned decarboxylation reaction, the quinaldine derivative and trimellitic anhydride are prepared in advance.
It is also conceivable to first maintain this mixture at a temperature at which only the decarboxylation reaction of the quinaldine derivative occurs, and then further heat the mixture to carry out the reaction. In these methods, the reaction is carried out using an inert solvent such as trichlorobenzene, but since the product quinophthalone compound has low solubility, most of it usually precipitates as crystals during the reaction step.

However, the crystals obtained here are fine and have poor filterability, which has the disadvantage that it takes a long time to filter the mixture after the reaction.

In view of the above-mentioned circumstances, the present inventors, in producing the quinophthalone compound represented by the forefoot structural formula [11],
As a result of various studies aimed at obtaining crystals with good filterability due to the size of the crystals, the present inventors discovered that the crystals obtained by the reaction can be significantly improved by carrying out the reaction using a specific method, and have completed the present invention. .

That is, the gist of the present invention is a method for batchwise production of a quinophthalone compound represented by the forefoot structural formula (II) using a quinaldine derivative represented by the forefoot structural formula [■] and trimellitic anhydride as raw materials. At least the quinaldine derivative is continuously or intermittently supplied into an organic solvent heated to a temperature of ~ The present invention relates to a method for producing a quinophthalone compound, which is characterized by carrying out the following reaction.

The present invention will be explained in detail below.

In the present invention, the quinaldine derivative of the forefoot structural formula [I] and trimellitic anhydride are reacted in a batchwise manner in an organic solvent. 7 to 2 times the mole, preferably 7
．． It is 2 to 7.3 times the mole.

The reaction temperature in the present invention is /10-2'1θ°C, preferably /90-3θ°C. If the reaction temperature is slightly lower, the decarboxylation reaction of the quinaldine derivative will occur.
If the reaction between the quinaldine derivative and trimellitic anhydride does not proceed well, and on the other hand, the reaction is too high, decomposition of trimellitic anhydride will occur, which is not preferable. TFC, the reaction pressure may be either normal pressure or increased pressure. ``The reaction time is usually about 1 to 20 hours, preferably about 7 to 15 hours.

Examples of the organic solvent used in the present invention include trichlorobenzene, nitrobenzene, g'-/thyl-copyrrolidone, acenaphthene, monochloronaphthalene, and dichloronaphthalene, and usually those having a boiling point higher than the reaction temperature are used. However, it is attractive because the reaction can be carried out at normal pressure. The amount of organic solvent used is usually 4 to 2 times by weight, preferably 7 to 3 times the weight of trimellitic anhydride.
It is twice the weight.

In the present invention, it is necessary to carry out the reaction while supplying at least one of the raw materials, the quinaldine derivative, into an organic solvent heated to the reaction temperature.

Ru. Specifically, for example, a method of carrying out a reaction while supplying a quinaldine derivative to a mixture of trimellitic anhydride dissolved in an organic solvent at a predetermined reaction temperature, or
Examples include a method in which the reaction is carried out while supplying both trimellitic anhydride and the quinaldine derivative into an organic solvent heated to a predetermined temperature, and the former method is particularly preferred.

In the present invention, the quinaldine derivative supplied into the reaction system immediately undergoes a decarboxylation reaction and simultaneously reacts with trimellitic anhydride to form a quinophthalone compound having the forefoot structural formula [1]. .

The quinaldine derivative is supplied as a powder or a solution or suspension in an organic solvent, and the supply method may be continuous or intermittent. Although the supply rate of the quinaldine derivative varies depending on the reaction conditions, it is desirable to lower the concentration of unreacted quinaldine derivative in the reaction system. n) 41 so that no more than f weight %, preferably substantially no unreacted quinaldine derivative is present. Furthermore, when it is supplied together with hydrothermal trimellitic acid, it is usually preferable to supply approximately equimolar amounts at the same time.

When the reaction is carried out by the reaction operation as described above,
Since the produced quinophthalone compound has low solubility in an organic solvent, most of the quinophthalone compound is usually precipitated as crystals at the end of the reaction. The crystal grains obtained by the method of the present invention have a large particle size and extremely excellent filterability.

On the other hand, for example, as shown in Comparative Example below, when a quinaldine derivative and trimellitic anhydride are dissolved in an organic solvent and reacted in advance, crystals with good filterability cannot be obtained. Although the reason for this is not clear, the X-ray diffraction diagram of the crystal obtained by the method of the present invention shows the peak shown in Figure 1, whereas the X-ray diffraction diagram of the crystal obtained by the method of the comparative example shows The crystal forms of the two are clearly different, as shown in Figure 2.

After the reaction, the mixture contains the front leg structural formula [11
) Most of the quinophthalone compounds are precipitated as crystals, but this mixture will solidify if it is cooled to 70°C or below, so it is common to add methanol, ethanol, dimethylformamide, dimethyl sulfoxide, etc. to the mixture. After diluting the mixture by adding an organic solvent with low solubility, the mixture is cooled to a temperature of 50° C. or lower, and the mixture is then filtered to recover crystals of the desired product. Further, the collected crystals are washed with water, methanol, dimethylformamide, etc., if necessary.

As described above, according to the present invention, crystals of the quinaldine derivative having the forefoot structural formula [1] can be obtained with good crystallization by a specific operating procedure. Furthermore, according to the present invention, there is also the effect that highly purified crystals can be obtained at a higher yield.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Example/ θ! with heating device and stirrer! 31. Charge trichlorobenzene cog θtxe into a reactor, and add trimellitic anhydride (for reagent) to this. ．． 9 f ((7,/9.2
After adding and dissolving quinaldine derivative (for reagent) with the forefoot structural formula [ID], the solution was heated to 2°C and stirred at the same temperature. /, A r CO, /! A mol) was gradually added over 7θ hours, and the reaction was continued for an additional 2 hours.

The reaction mixture was cooled to 7 q'ci, then methanol t/me was added over one hour, stirred at the same temperature for one hour, cooled to 30°C,
m) at 5θOrrrmH? The mixture was filtered under reduced pressure.

The particle size (length), purity, and yield to the quinaldine derivative of the thus recovered crystals were determined, and the time required for filtration was also measured.

The X-ray diffraction pattern of the recovered crystals was as shown in FIG.

Comparative Example 1 In the method of Example, trichlorobenzene, trimellitic anhydride and a quinaldine derivative were charged in advance into a reactor, and this mixture was first stirred at a temperature of 770°C for 3 hours. The results are shown in Table 1 in the same manner as in Example 1 except that the decarboxylation reaction was carried out, and then the temperature was raised to 10° C. and the reaction was carried out for 100 hours under stirring.

Moreover, the X-ray diffraction pattern of the crystal obtained by this method was as shown in FIG.

Comparative Example 1 In the method of Example 1, trichlorobenzene and a quinaldine derivative were charged in advance in a reactor, and the mixture was first stirred at a temperature of 100°C for 3 hours to carry out a decarboxylation reaction of the quinaldine derivative. , then 210°C
and at the same temperature with stirring, add 70
Table 1 shows the results obtained when all treatments were carried out in the same manner as in Example 1, except for rc, in which the reaction was carried out by gradually adding the compound over time and holding it for Ω hours.

Table 1

[Brief explanation of the drawing]

Figure 1 shows the X-ray diffraction diagram of the crystal obtained by the method of Example 1, and Figure 2 shows the X-ray diffraction diagram of the crystal obtained by the method of Comparative Example/.The horizontal axis is the diffraction angle ( The vertical axis shows the diffraction intensity. Applicant Mitsubishi Kasei Ko 1100 Co., Ltd. Agent
Patent attorney Haseyo = (7 others)

Claims (1)

[Claims] (1) In a method for batchwise production of a quinophthalone compound represented by the following structural formula [■] using a quinaldine derivative represented by the following structural formula [I] and trimellitic anhydride as raw materials,
While the quinaldine derivative is continuously or intermittently supplied into an organic solvent heated to a temperature of IO° C., the quinaldine derivative and anhydrous trimelite are simultaneously decarboxylated and decarboxylated. A method for producing a quinophthalone compound, which is characterized by carrying out a reaction with an acid.