JPS5838468B2 - Kinophthalon Keikagobutsu no Seizouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a method for producing a novel quinophthalone compound.

More specifically, it is a method for producing a quinophthalone compound suitable for use as a pigment particularly having excellent light resistance and heat resistance.

Although many compounds have been known as quinophthalone compounds, compounds with particularly excellent light resistance and heat resistance that are suitable for use as pigments are not well known**.

That is, for example, a quinophthalone compound represented by the following formula (IV) [wherein Y is a halogen atom, X, Xl, and X2 are hydrogen atoms or halogen atoms, and n is an integer of 1 to 4] has been proposed Japanese Patent Publication No. 1973-3
0,736, JP-A-48-32,916), but the heat resistance was still not necessarily sufficient, and it was necessary to further halogenate the heat resistance. .

As a result of intensive research into a method for providing a quinophthalone compound that overcomes these drawbacks, has excellent heat resistance and color tone, and also has improved heat resistance, the present inventor has developed a new compound represented by the above formula [■] industrially. The present invention was achieved by researching an advantageous manufacturing method.

That is, the present invention provides the following formula (I) [wherein A may be substituted with a non-ionizable substituent and is bonded at the ortho or peri position of the two carbonyl groups (1 and 2)] phenylene group or naphthylene group, X is a non-ionizable substituent, n is an integer of O to 3]. * [In the formula, R is a hydrogen atom, a carboxyl group, or a halogen atom, Y is a substituent that does not ionize, and m is an integer of 1 to 4] It is characterized by being heated and reacted with a quinoline derivative represented by the following, and further halogenated if desired. The following formula CIII is
) [In the formula, A, X, Y, m and n are the same as in the above formula, R' is a hydrogen atom or a halogen atom] A method for producing a quinophthalone compound or a further halogenated quinophthalone compound represented by the following: .

The naphthalene-2°3-dicarboxylic acids or their 2,3-dicarboxylic anhydrides used in the method of the present invention are represented by the above formula [■].

In the formula, A may be substituted with a non-ionizable substituent, and may be substituted with the two carbonyl groups (numbered 1 and 2 in the formula) forming the imide ring at the ortho position or periposition. It is a phenylene group or a naphthylene group bonded at a position, X is a non-ionizable substituent, and n is an integer of O to 3.

A substituent that does not ionize means a group that does not react with an alkali to form a water-soluble salt, such as a carboxylic acid group or a sulfonic acid group, and specifically includes chlorine, bromine, etc. Halogen atoms such as methyl group, ethyl group, propyl group, alkyl group such as butyl group, alkoxy group such as methoxy group, ethoxy group, allyl group such as phenyl group, tolyl group, acyl group such as benzoyl group, acetyl group etc. can be cited as preferable.

Specific examples of such compounds include, for example, and compounds in which the benzene ring or naphthalene ring constituting the phthalimide group or naphthoylimide group of these compounds is substituted with 1 to 4 halogen atoms, particularly chlorine or bromine atoms; , and the benzene ring or naphthalene ring constituting the phthalimide group or naphthoylimide group of these compounds is 1
~ Compounds corresponding to those substituted with 4 halogen atoms, especially chlorine or bromine atoms, and compounds in which the benzene ring or naphthalene ring constituting the phthalimide group or naphthoylimide group of these compounds is substituted with 1 to 4 halogen atoms, especially chlorine or bromine atoms. Compounds corresponding to those substituted with bromine atoms, and further bromine atoms of compounds represented by the above formulas (
That is, examples include compounds in which the bromine atom (at the 2,3-naphthalene dicarboxylic acid moiety) is replaced with a chlorine atom.

These compounds are 5-amino- or 6-amino-2,3
- Naphthalenedicarboxylic acid or a halogenated derivative thereof, phthalic anhydride, 2,3-naphthalenedicarboxylic anhydride, L2-naphthalenedicarboxylic anhydride, 1,
It can be synthesized by subjecting 8-naphthalic anhydride or a halogenated derivative thereof to a heating reaction, and optionally further halogenating it.

In addition, examples of the quinoline derivatives used in the method of the present invention include 3-oxyquinaldine, 3-oxyquinaldine-4-carboxylic acid, 3-oxy-4-bromoquinaldine, 3-oxy-4-chloroquinaldine, 3-oxy-6-bromoquinaldine, 3-oxy-6-chloroquinaldine, 3-oxy-8-bromoquinaldine, 3-
Oxy-8-chloroquinaldine, 3-oxy-4,6-
Dibromoquinaldine, 3-oxy-6,8-dibromoquinaldine, 3-oxy-4-bromo-6-chloroquinaldine, 3-oxy-6,8-dichloroquinaldine, 3-
Oxy-6-promuquinaldine-4-carboxylic acid, 3-
Oxy-6,7-dichloroquinaldine, 3-oxy-5
, 6-dichloroquinaldine and the like are preferred.

The reaction of the invention can be carried out in the presence or absence of a solvent.

When the reaction is carried out in the presence of a solvent, the solvent used may be an organic solvent inert to the reaction, such as nitrobenzene,
O-nitrotoluene, O-diclobenzene, trichlorobenzene, trimethylbenzene, decalin, tetralin, chlornaphthalene, N-methylpyrrolidone, dimethylacetamide, etc. are used.

The amount used may be 2 to 20 times the weight of the reactants,
Although a larger amount of solvent may be used, from the viewpoint of recovering the solvent after the reaction, it is preferably 3 to 15 times the amount by weight.

Moreover, imidized naphthalene represented by the above formula [I]
The ratio of the 2,3-dicarboxylic acids or their 2,3-dicarboxylic anhydrides to the quinoline derivative represented by the above formula (II) may be within any range; In order to efficiently react the quinoline derivative, it is better to use an excess of the naphthalene-2,3-dicarboxylic acid derivative or its anhydride since it is easily decomposed compared to the quinoline derivative.

For example, the amount used is 2 to 20 times the mole of the quinoline derivative.

The reaction may be carried out at a temperature in the range of 100 to 300°C, preferably in the range of 160 to 260°C.

The reaction is carried out by mixing the raw material mixture in the presence or absence of the above solvent,
The process can proceed simply by heating at an appropriate temperature, but in order to be more effective, a catalyst such as zinc chloride, aluminum chloride, or a boron fluoride-ether complex may be added.

As detailed above, according to the present invention, quinophthalone compounds, which are new compounds, can be produced extremely easily, and these compounds have excellent heat resistance and color tone, making them particularly useful as pigments. It is possible to provide a compound and its effects are canine.

Hereinafter, the method of the present invention will be explained in detail with reference to Examples.

In the examples, "parts" represent "parts by weight."

Example 1 (1) 20 f of naphthalene-2,3-dicarboxylic acid was added to 60 yd of nitric acid with a specific gravity of 1.42 at room temperature, and the mixture was kept at 100°C for 1 hour.

After that, water was added, filtered, washed with water, and dried to obtain pale yellow crude compound 23.
1 (yield 97φ) was obtained.

Recrystallization from glacial acetic acid gave pale yellow prismatic crystals of 5-nitro-2,3-naphthalene dicarboxylic acid with a melting point of 238°C.

(2) 14 g of 5-nitro-2,3-naphthalene dicarboxylic acid was mixed with ammonia water (100 liters of 28% ammonia water)
To this was added a hot solution of crystalline ferrous sulfate 1221 dissolved in 200 rr of water, and heated in a steam bath for 30 minutes.

After that, the product was filtered while hot, 50rrll of glacial acetic acid was added to the filtrate, and it was left to stand for 12 hours. The precipitate was collected in an oven, washed with water, and dried to obtain a crude compound of 8.6f (yield 69.7%). Ta.

Recrystallization was performed from 75φ acetic acid to obtain 5-amino-2,3-naphthalene dicarboxylic acid having a melting point of 360° C. or higher and having the following elemental analysis values.

CHN Theoretical value (to) 62.30 3.90 6.06
Actual sail value 61.35 4.01 5.69 (3
) 5-amino-2,3- produced as in (2) above
Naphthalene dicarboxylic acid 9.2 P (0.04 mol)
and phthalic anhydride 6f (0.04 mol) were dissolved in glacial acetic acid and heated under reflux for 2 hours.

Thereafter, the precipitate was poured into ice water and the precipitate was collected, washed with water, and dried to obtain a crude compound 81 (yield: 56φ).

This was recrystallized from 65 g of glacial acetic acid to obtain 5-phthalimino-naphthalene-2,3-ycarboxylic acid having a melting point of 300 DEG C. or higher.

In addition, various iminated naphthalene-2,3-dicarboxylic acids as shown in Table 1 were synthesized in the same manner as in steps (1) to (3) above.

The yield, melting point, and elemental analysis values are shown in Table 1.

Moreover, these 2,3-dicarboxylic acid anhydrides were produced by heating and refluxing the corresponding 2,3-dicarboxylic acids in acetic anhydride for 1 hour.

(4) 11 parts of 5-phthaliminonaphthalene-2,3-dicarboxylic anhydride and 2-methyl-3-oxyquinoline-
6.2 parts of 4-carboxylic acid in 60 parts of nitrobenzene
After heating under reflux for an hour, the mixture was cooled, and the solvent was removed by steam distillation.

The precipitate was collected in an oven, washed with ethanol, and dried to obtain 7.0 parts of a yellow product having the following structure.

The melting point of the product recrystallized from xylene was determined by differential thermal analysis (D
According to TA), the temperature was 488°C.

The elemental analysis values are shown in Table 2 below, and were consistent with the calculated values.

Also, this stuff is dimethylformamide The maximum absorption wavelength in (DMF) was 462 mμ.

This product can be used as a coloring pigment as it is by finely pulverizing it, but it was further made into a pigment by dissolving it in sulfuric acid, pouring it into ice water, reprecipitating it, and washing it with water.

This pigment has excellent light resistance, heat resistance, and chemical resistance, and is suitable for coloring printing ink paints, plastics, etc.

Example 2 5-(2,3'-naphthalimino)naphthalene-2,3
- 12.7 parts of dicarboxylic anhydride and 6.2 parts of 2-methyl-3-oxyquinoline-4-carboxylic acid were heated under reflux for 6 hours in 60 parts of nitrobenzene, then cooled, and the solvent was distilled off by steam distillation. I left.

The precipitate was collected in an oven, washed with ethanol, and dried to obtain 8.3 parts of a yellow product having the following structure.

The melting point of the product recrystallized from N-methylpyrrolidone is 36
The temperature was 0°C or higher.

Moreover, the maximum absorption wavelength in DMF was 462 mμ.

The elemental analysis values are shown in Table 3 below, and were almost in agreement with the calculated values.

Example 3 5-tetrabromophthalimino-naphthalene-2,3-
21.0 parts of dicarboxylic acid anhydride and 6.2 parts of 2-methyl-3-oxyquinoline-4-carboxylic acid were heated under reflux for 8 hours in 100 parts of trichlorobenzene, and the resulting precipitate was collected. After washing with ethanol and drying, 12.3 parts of a product having the following structural formula were obtained.

The melting point of the product purified by hot washing with trichlorobenzene was 360°C or higher.

The maximum absorption wavelength in DMF was 464 mμ.

The elemental analysis values are shown in Table 4 below, and were almost in agreement with the calculated values.

Example 4 5-tetrachlorophthalimino-naphthalene-2,3-
15.4 parts of dicarboxylic acid anhydride and 6.2 parts of 2-methyl-3-oxyquinoline-4-carboxylic acid were heated under reflux for 8 hours in 100 parts of trichlorobenzene, and then cooled, and the resulting precipitate was collected in an oven. After washing with ethanol and drying, 10.2 parts of a product having the following structural formula was obtained.

The melting point of the product purified by hot washing with trichlorobenzene was 430° C. according to DTA.

Moreover, the maximum absorption wavelength in DMF was 462 mμ.

The elemental analysis values are shown in Table 5 below, and were consistent with the calculated values.

Example 5 20 parts of 5-(5',8'-dibromonaphthalimino)naphthalene-2,3-dicarboxylic anhydride and 6.2 parts of 2-methyl-3-oxyquinoline-4-carboxylic acid were added to 100 parts of nitrobenzene. The mixture was heated under reflux for 8 hours and then cooled, and the resulting precipitate was collected in a furnace and washed with ethanol to obtain 14 parts of a product having the following structural formula.

The melting point was 442°C according to DTA.

The maximum absorption wavelength in input DMF was 462 mμ.

The elemental analysis values are as shown in Table 6 below, and the calculated values are V. Example 6 5-(5',6',7',8'-tetrabromonaphthalimino)naphthalene-2,3-dicarboxylic anhydride 50 things
and 7 parts of 2-methyl-3-oxyquinoline-4-carboxylic acid were heated under reflux in 150 parts of nitrobenzene for 8 hours, then cooled and the resulting precipitate was collected in an oven, washed with ethanol, and prepared as follows. 20 parts of a product having the structural formula were obtained.

The melting point of this product was 500° C. or higher according to DTA.

Moreover, the maximum absorption wavelength in DMF was 467 mμ.
The elemental analysis values are shown in Table 7 below, and were consistent with the calculated values.

Example 7 5-(1', 2'-naphthalimino)naphthalene-
12.7 parts of 2,3-dicarboxylic anhydride and 2-methyl-
6.2 parts of 3-oxyquinoline-4-carboxylic acid was heated under reflux for 6 hours in 60 parts of nitrobenzene, then cooled, and the resulting precipitate was collected in an oven, washed with ethanol, and dried to obtain a melting point having the following structure. 7.7 parts of a yellow product with a temperature of 360° C. or higher was obtained.

The elemental analysis values are shown in Table 8 below, and were almost in agreement with the calculated values.

Example * 12.7 parts of 5-(1', 8'-naphthalimino)-naphthalene-2,3-dicarboxylic anhydride and 6.2 parts of 2-methyl-3-oxyquinoline-4-carboxylic acid were added to 60 parts of nitrobenzene. The mixture was heated under reflux for 6 hours, then cooled, and the resulting precipitate was collected in a furnace, washed with ethanol, and dried to obtain 7.5 parts of a yellow product having the following structure and a melting point of 360° C. or higher.

The elemental analysis values are shown in Table 9 below, and were almost in agreement with the calculated values.

Example 9 1-0 parts of the product obtained by the method of Example 1 (4) and 〇-
100 parts of dichlorobenzene was mixed, heated to 160°C, and 6.4 parts of bromine was added dropwise while stirring.

After the addition was completed, the reaction was continued for another 2 hours, and then cooled, and the product was filtered, washed with ethanol, and dried to obtain 12 parts of a yellow product having the following structural formula and a melting point of 360° C. or higher.

The elemental analysis values were as shown in Table 10 and almost agreed with the calculated values.

Example 10 8-bromo-5-(2',3'-naphthalimino)
-25 parts of naphthalene-2,3-dicarboxylic anhydride and 2
- 10 parts of methyl-3-oxyquinoline-4-carboxylic acid is heated under reflux in decalin for 20 hours and then cooled, the resulting precipitate is separated in a furnace, washed with ethanol and dried to give a melting point of 360.
12 parts of a yellow product represented by the following structural formula was obtained.

The elemental analysis values are shown in Table 11 below, and were almost in agreement with the calculated values.

Example 11 5-(2',3'-naphthalimino)-naphthalene-2
, 20 parts of 3-dicarboxylic anhydride and 9 parts of 6-bromo-2-methyl-3-oxyquinoline-4-carboxylic acid were heated under reflux for 20 hours in decalin, then cooled, and the resulting precipitate was separated in a furnace. After washing with ethanol and drying, 9 parts of a yellow product having a melting point of 360° C. or more and represented by the following structural formula were obtained.

The elemental analysis values almost agreed with the calculated values as shown in Table 12 below.

Example 12 8-bromo-5-(2',3'-naphthalimino)-
20 parts of naphthalene-2,3-dicarboxylic anhydride and 6-
10 parts of bromo-2-methyl-3-oxyquinoline-4-carboxylic acid is heated under reflux in decalin for 20 hours, then cooled and the resulting precipitate is separated in a furnace, washed with ethanol and dried to give a melting point of 360°C or higher. 11 parts of a yellow product represented by the following formula were obtained.

Elemental analysis values are in the table below. Agreed.

13, calculated values and approximate examples 13 30 parts of 5-(5',8'-dibromonaphthalimino)-naphthalene-2,3-dicarboxylic anhydride and 2,6-dimethyl-3-oxyquinoline-4 - 10 parts of carboxylic acid was heated under reflux in nitrobenzene for 8 hours and then cooled, the resulting precipitate was collected in an oven and washed with ethanol to obtain 15 parts of a yellow product having the following structure and a melting point of 360°C or higher. Ta.

The elemental analysis values are shown in Table 14 below, and were almost in agreement with the calculated values.

The products obtained in Examples 2 to 13 can be used as they are as a coloring agent by finely pulverizing them, but they can be further precipitated by dissolving them in sulfuric acid and placing them in ice water, followed by washing with water. It is turned into a pigment.

The maximum absorption wavelengths of the products obtained in Examples 7 to 13 are as follows: Product of Example 7 462 nm Product of Example 8 463 nm Product of Example 9
465 nm Product of Example 10 4
63 nm Product of Example 11 465 nm
Product of Example 12 466 nm Example 13
The product of 463 nm is as follows.

This pigment has excellent light resistance, heat resistance, and chemical resistance, and has also been found to be suitable for coloring printing inks, paints, and plastics.

Claims (1)

[Claims] 1 The following formula (I) phenylene group or naphthylene group, X is a halogen atom, n is an integer of O to 3] Naphthalene-2,3-dicarboxylic acids or their 2,3-dicarboxylic acid anhydrides represented by the following formula (II) where R is a hydrogen atom, a carboxyl group or a halogen atom, Y is a halogen atom or a lower alkyl group, m is 1
An integer of ~4] The following formula (I[) is characterized by being heated and reacted with a quinoline derivative represented by the following formula, and optionally further halogenated [wherein A, X, Y, m and n are the same as in the above formula] , R' is a hydrogen atom or a halogen atom.] A method for producing a quinophthalone compound or a further halogenated quinophthalone compound.