JPS6027694B2 - Method for producing quinophthalones - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing quinophthalone or a derivative thereof.

More specifically, the present invention relates to a method for producing quinophthalone or a derivative thereof, which is characterized by using a specific solvent. Conventionally, trichlorobenzene, tall oil, and N-methylpyrobenzene have been used as reaction solvents for producing quinophthalone or its derivatives by condensing 2-methylquinoline or its derivatives with phthalic acid, its anhydride, or its derivatives. High boiling point solvents such as dorine, diphenyl, diphenyl ether, diphenylene oxide, acenaphthene, monochloronaphthalene, and dichloronaphthalene are known.

However, when these solvents are used, the quality and yield of the target quinophthalones are not sufficient, and furthermore, the solvents themselves have health and safety issues, so these solvents are not used. The method used was not industrially satisfactory. Furthermore, alkylbenzenes such as butylbenzene and isopropylxylene can also be used as reaction solvents.

However, although these solvents reduce safety and health problems, the quality and yield of the target quinophthalones are insufficient, and they are still not industrially satisfactory. As a result of intensive research into the above-mentioned problems, the present inventors have found that by conducting the reaction in an alkylbenzene solvent with a specific structure, the desired product, quinophthalones, can be produced more easily than the production method using conventional solvents. They found that the quality and yield of these products could be excellent, and completed the present invention.

That is, the present invention provides 2-methylquinoline or its derivatives represented by the structural formula (1) (hereinafter referred to as "quinolines"), and phthalic acid represented by the structural formula (〇), its derivatives, or their anhydrides (hereinafter referred to as "quinolines"). "phthalic acids") is represented by the general formula (m) (wherein R,, R2, and R3 are alkyl groups, and the total number of carbon atoms in R., R2, and R3 is 9 or less). The present invention relates to a method for producing quinophthalone or a derivative thereof (hereinafter referred to as "quinophthalones") represented by the structural formula (W), which is characterized by condensation in alkylbenzene.

To explain the present invention in more detail, the quinolines include 3-hydroxy-2-methylquinolines of the following general formula.

That is, it also includes compounds represented by (wherein R4 represents a hydrogen atom or a carboxyl group, and R5 and R6 represent a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxyl group).

Specific examples of the above 3-hydroxy-2-methylquinolines include 3-hydroxy-2-methylquinoline, 3-hydroxy-2-methylquinoline-4-carboxylic acid,
-chloro-3-hydroxy-2-methylquinoline-4-carboxylic acid, 5-chloro-3-hydroxy-2-methylquinoline, 6-chloro-3-hydroxy-2-methylquinoline-4-carboxylic acid, 7-bromo-3-hydroxy-2-methylquinoline-4-carboxylic acid, 8-chloro 3-hydroxy-2-methylquinoline-4-carboxylic acid, 5,8-dichloro-3-hydroxy-2-methylquinoline-4-carboxylic acid, 6,7-dibromo-3-hydroxy-2-methylquinoline-4-carboxylic acid, 6,8-
Dichloro-3-hydroxy-2-methylquinoline-4-carboxylic acid, 2,6-dimethyl-3-hydroxyquinoline-4-carboxylic acid, 3-hydroxy-2,5,8-trimethylquinoline-4-carboxylic acid, 6-ethyl-3-hydroxy-2 -Methylquinoline, 3-hydroxy-6
-methoxy-2-methylquinoline, 6-ethoxy-3-hydroxy-2-methylquinoline-4-carboxylic acid, 5
-chloro-2,6-dimethyl-3-hydroxyquinoline-4-carboxylic acid, 7-chloro-2,8-dimethyl-3
-hydroxyquinoline-4-carboxylic acid and the like.

In addition to these quinolines, sulfonated compounds and the like are also included.

The phthalic acids mentioned above include trimellitic acid or its anhydride represented by the following structural formula, and further include halogenophthalic acid or its anhydride.

In addition, as the quinolines, the above-mentioned 3-hydroxy-2
- When methylquinolines and the above trimellitic acid as a phthalic acid are condensed in a solvent represented by the general formula (m), the following general formula (wherein R5 and R6 are hydrogen atoms,
3'-hydroxyquinophthalone-4-carboxylic acids represented by a halogen atom, a lower alkyl group, or a lower alkoxyl group can be obtained in high yield and quality.

In the condensation reaction of the present invention, for example, 1 mole of the quinoline and 1.0 to 1.2 mole of the phthalic acid are mixed into 1 to 2 moles of alkylbenzene represented by the general formula (m) at a concentration of 180 to 310%.
qo, preferably 190 to 250 qo.

At this time, if necessary, pressure may be applied using heated solvent vapor or an inert gas such as nitrogen gas. After reacting for 1 to 1 hour, the precipitate is taken out in a furnace by cooling to about 60 oo, and methanol ,
By washing with water and drying, the quinophthalones, which are the object of the present invention, can be obtained in high yield. The general formula (
R in m). , R2 and R3 may be selected arbitrarily, but it is preferable that R, , R2 is a methyl group or ethyl group, and R8 is a methyl group, ethyl group, propyl group or butyl group.

For example, rt-butylbenzene, tert-amylbenzene, tert-hexylbenzene, or tert-butylbenzene.
Heptylbenzene and the like are preferred. However, tert-butylbenzene has a boiling point of 169°C to 170°C and a flash point of 4°C, whereas tert-amylbenzene has a boiling point of 19°C to 0°C and a flash point of 1°C.
-Hexylbenzene has a boiling point of 205 to 21,000 (
Furthermore, rt-heptylbenzene has a boiling point of 22yC to 230°C (depending on the isomer).

On the other hand, since the condensation reaction for producing quinophthalones of the present invention is carried out by heating to 180°C to 310 qo as described above, it is necessary to apply pressure when the reaction is carried out above the boiling point of the solvent. .

Furthermore, even if pressure is applied, it is desirable from the standpoint of equipment and operation that the degree of pressurization be as low as possible. Furthermore, since heating is required, from the viewpoint of disaster prevention, the higher the flash point of the solvent, the safer it is. From the above points, more preferable alkylbenzenes of the general formula (m) include rt-amylbenzene, rt-hexylbenzene, and te-heptylbenzene.

In addition, the total number of carbon atoms of R, R2, and R3 in the general formula (m) is up to 9, but if the number of carbon atoms is larger than this, the solubility for quinolines and phthalates is poor, so it is used as a reaction solvent. It is inappropriate to do so.

In the alkylbenzene represented by the general formula (m), the alkyl group is bonded to the benzene nucleus through a tertiary carbon, so that deterioration does not easily occur when a solvent is repeatedly used.

That is, the production of peroxide due to deterioration of the solvent and the production of tar-like substances due to decomposition and recombination of the peroxide are not observed. Therefore, deterioration in quality such as a decrease in yield or a decrease in purity or sharpness of the pigment due to adsorption of deterioration products of the solvent to the reactant does not occur. Such deterioration of the solvent was unavoidable with the alkylbenzene solvents commonly used in the past. Further, the solvent of general formula (m) can be obtained from a synthetic material in the petrochemical industry and has the economical advantage of being inexpensive.

When the solvent represented by the general formula (m) is used in the method of the present invention, there are fewer side reactions and a greater ability to dissolve various reaction by-products than in the condensation reaction in conventionally known reaction solvents. Therefore, extremely pure quinophthalones can be obtained in high yield.

Furthermore, since the solvent has almost no odor and has excellent oxidation resistance, it can be used repeatedly after undergoing a solvent recovery process. Therefore, the solvent represented by the general formula (m) can be said to be an excellent solvent for producing quinophthalones. Next, the method of the present invention will be further explained by examples.

Example 1 20.3 hours of 3-hydroxy-2-methylquinoline-4-carboxylic acid and 19.2 hours of trimellitic anhydride were prepared at RT.
- Added to 150 amylbenzenes and heated at 190oC for 4 hours.

Thereafter, the precipitate was cooled to about 60q0, separated by furnace, washed with methanol and water, and dried to obtain 3'-hydroxyquinophthalone-4-carboxylic acid 32. represented by the following structural formula.
0 pm (theoretical yield 95%, melting point 350 pm or more) was obtained.

Example 2 15.9 hours of 3-hydroxy-2-methylquinoline and 19.2 hours of trimellitic anhydride were mixed into the following composition (*) at rt.
-130 units of hexylbenzene [in addition to 4 units of 205 q0
heated for an hour.

Thereafter, the precipitate was cooled to about 60 mm, heated in an oven, washed with methanol and water, and dried to give 31.0 mm of 3''-hydroxyquinophthalone-4-carboxylic acid, the same as in Example 1 (theoretical yield: 93 mm). %, melting point 350°C or higher).
- Composition of hexylbenzene 1,1-dimethyl-butylbenzene 42wt% 1,1,
2-trimethyl-propylbenzene 42wt
% 1-Ethyl-1-methyl-propylbenzene 16 wt% Example 3 3-hydro.

An alkylbenzene (*) of the following composition was prepared by combining 15.9 mm of 2-methylquinoline and 19.2 mm of trimellitic anhydride.
150 and heated at 20yo for 3 hours. Approximately 60
After cooling to 0.00, the precipitate was collected in a furnace, washed with methanol and water, and dried to give 31.0 g of the same 3'-hydroxyquinophthalone-4-carboxylic acid as in Example 1 (theoretical yield: 93%).
, a melting point of 350oC or higher) was obtained. (*) Compositional boiling point of alkylbenzene 195-230℃ rt-amylbenzene % r
t-hexylbenzene 55 M% to rt-hexylbenzene 22 M%te-octylbenzene 1 wt%Example 4 15.9 m of 3-hydroxy-2-methylquinoline and 19.2 m of trimellitic anhydride to rt- In addition to 180 decanylbenzene (boiling point 265-280oo), 250
It was heated for 1 hour in the afternoon.

Thereafter, the precipitate was cooled at about 60:00, and the precipitate was taken up in the furnace, washed with methanol and water, and then dried. %, melting point 350°C or higher). Example 5 21.7 parts of 2,6-dimethyl-3-hydroxyquinoline-4-carboxylic acid and 19.2 parts of trimellitic anhydride were added to 180 parts of a solvent having the same composition as in Example 3, and at 205 parts, Heated for 3 hours.

Thereafter, the precipitate was cooled to about 6,000, taken out in a furnace, washed with methanol and water, and dried.
-Hydroxy-6'-methylquinophthalone-4-carboxylic acid 31.9 hours (theoretical yield 91%, melting point 350°C or higher)
I got it.

Comparative Example 1 20.3 hours of 3-hydroxy-2-methylquinoline-4-carboxylic acid and 19.2 hours of trimellitic anhydride were mixed in 1,2
, 130 qo of 4-trichlorobenzene, plus 205 qo
It was heated for 3 hours.

The precipitate was cooled to about 60 mm, taken out in a furnace, washed with methanol and water, and dried to give 25.0 mm of 3-hydroxyquinophthalone-4-carboxylic acid (theoretical yield: 75%), the same as in Example 1.
A melting point of 350 qo or more was obtained.

Claims (1)

[Claims] 1. 2-methylquinoline or a derivative thereof represented by the structural formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼;
Structural formula (II)▲There are mathematical formulas, chemical formulas, tables, etc.▼ Phthalic acid, its derivatives, or their anhydrides represented by general formula (III)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (wherein, R_1, R_2, R_3 are alkyl groups, and the total carbon number of R_1, R_2, R_3 is 9 or less) Structural formula (IV) characterized by condensation in an alkylbenzene represented by ▲There are mathematical formulas, chemical formulas, tables, etc. ▼Production method of quinophthalone or its derivatives. 2 In the general formula (III), R_1 and R_2 are a methyl group or an ethyl group, R_3 is a methyl group, an ethyl group,
The method for producing quinophthalone or a derivative thereof according to claim 1, which is a propyl group or a butyl group. 3. Quinophthalone or its quinophthalone according to claim 1, wherein the alkylbenzene represented by the general formula (III) is any one of tert-butylbenzene, tert-amylbenzene, tert-hexylbenzene, and tert-heptylbenzene. Method for producing derivatives. 4 The derivative of 2-methylquinoline of the above structural formula (I) has the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_4 represents a hydrogen atom or a carboxyl group, R_5 and R_6 represent a hydrogen atom, The method for producing a quinophthalone derivative according to any one of claims 1 to 3, which is a 3-hydroxy-2-methylquinoline represented by a halogen atom, a lower alkyl group, or a lower alkoxyl group. 5. Claims 1 to 5, wherein the derivative of phthalic acid or its anhydride of the structure (II) is trimellitic acid or its anhydride represented by the following structural formula ▲ Numerical formula, chemical formula, table, etc. ▼ 4. A method for producing a quinophthalone derivative according to any one of Item 3. 6 The 2-methylquinoline derivative of the structural formula (I) is 3 represented by the general formula set forth in claim 4.
-Hydroxy-2-methylquinolines, wherein the phthalic acid derivative of the structural formula (II) or its anhydride is trimellitic acid or its anhydride represented by the structural formula of claim 8. Yes, and the structural formula (IV)
The derivative of quinophthalone represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (wherein R_5 and Q_6 represent a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxyl group) A method for producing a quinophthalone derivative according to any one of claims 1 to 3, which is a quinophthalone-4-carboxylic acid.