JPS5851024B2 - Yushiyokukagobutsunoseizouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of novel colored compounds.

More specifically, the present invention relates to a method for producing quinophthalone colored compounds suitable for use as dyes and pigments with particularly excellent heat resistance.

Although many compounds have been known as quinophthalone compounds, methods for producing compounds suitable for use as dyes and pigments, particularly those having excellent heat resistance and light resistance, are not well known.

The present inventors believe that if a certain specific compound is reacted, the formula (m) (wherein A and B are a benzene ring which may be substituted with a halogen atom, and X is a benzene ring which may be substituted with a nonionizable substituent) A phenylene group or a naphthylene group bonded at the ortho or peri position of two carbonyl groups.

) was obtained, and the present invention was accomplished by discovering that this compound is suitable for use as a dye and pigment with excellent heat resistance and light resistance.

That is, the present invention provides a quinoline derivative represented by the following general formula [■] * (wherein A and B are as described above). It is characterized in that it is heated to react with the dicarboxylic acids or carboxylic anhydrides thereof, and is further halogenated if desired.

This is a method for producing a colored compound represented by the following general formula (IID, where A, B, and X are as described above).

The compound represented by the general formula [■] produced by the method of the present invention may form the following resonance structure, but in the method of the present invention, the compound represented by the general formula [■] has all of these structural formulas, (Ha, l, [■], (III
b).

The quinoline derivative used in the method of the present invention is represented by the above general formula [■].

Specific examples of this compound include 8-(naphthalimino)-quinaldine, 8-(2-chlornaphthalimino)-quinaldine, 8-(2-promnaphthalimino)quinaldine, 8-(3-chlornaphthalimino) ) quinaldine, 8-(3-promnaphthalimino)quinaldine, 8
-(4-chlornaphthalimino)quinaldine, 8-(4
quinaldine, 8-(4-chlornaphthalimino)quinaldine, 8-(4-iodonaphthalimino)quinaldine, 8-(2,4-dichloronaphthalimino)quinaldine, 8-(3,5- dichloronaphthalimino)quinaldine, 8-(3,6-cyclonaphthalimino)quinaldine, 8-(4,5-dichloronaphthalimino)quinaldine, 8-(2,4-dibromnaphthalimino)quinaldine, 8-(2,5-dibromnaphthalimino)quinaldine, 8-(3,5-dibromnaphthalimino)quinaldine, 8-(3,6-dibromnaphthalimino)quinaldine, 8-(4,5- Dipromnaphthalimino)quinaldine, 8-(2,4,5-trichlornaphthalimino)quinaldine, 8-(3,4,5-trichlornaphthalimino)quinaldine, 8-(2,4,5-
Trichlornaphthalimino)quinaldine, 8-(2.4
・5-7-titrachlornaphthal)quinaldine, 8-(
2-3, 4, 5, 6, 7 hexachlornaphthalimino)
Quinaldine, 8-(2, 3, 4, 5, 6, 7 hexabromnaphthalimino) quinaldine, 8-(3-brome, 5
-chlornaphthalimino)quinaldine, 8-(3-chlor,5-promnaphthalimino)quinaldine, 8=(4
-bromo,5-chlornaphthalimino)quinaldine, 8
-(4-chlor, 5-iothonaphthalimino)quinaldine, 8-(3-7'rom, 5-iothonaphthalimino)
Quinaldine, 8-(4-chloro-5-chlornaphthalimino)quinaldine, 8-(2,4-dichlor,5-promnaphthalimino)quinaldine, 8-(2,4-dibrome, 5-chlornaphthalimino) ) There are many compounds such as quinaldine.

These compounds can be easily synthesized by heating and reacting 8-aminoquinaldine with 1,8-naphthalic anhydride or its halogenated derivative.

The dicarboxylic acids or dicarboxylic anhydrides used in the method of the present invention are represented by the above general formula [■], and specific examples of this compound include the following dicarboxylic acids and dicarboxylic anhydrides.

The reaction of the method of the present 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 is an organic solvent inert to the reaction, such as nitrobenzene, nitrobenzene, etc. =) lobenzene, ortho-
Dichlorobenzene, trichlorobenzene, trimethylbenzene, tecarin, tetralin, diphenyl ether,
Chlornaphthalene, N-methylpyrrolidone, etc. are used.

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

Further, the ratio of the imidized quinoline derivative represented by the above formula [■] to the dicarboxylic acid represented by the above formula (II) or its dicarboxylic acid anhydride may be in any range, but the preferred ratio of both is 0.3 to 0.3. A range of 3 is sufficient.

The reaction may be carried out at a temperature in the range of 100 to 300°C, preferably in the range of 150 to 250°C.

The reaction can proceed simply by heating the raw material mixture at an appropriate temperature in the presence or absence of the above solvent, or for more effective reaction, zinc chloride, aluminum chloride, boron trifluoride-ether complex, etc. can be used. This is done by adding a catalyst.

Furthermore, although the quinoline derivative represented by the general formula [I] is used as a raw material in the present invention, it is not necessary to isolate this raw material in advance, and 8-aminoquinaldine and 1.8
-naphthalic acid derivative or its acid anhydride derivative at 120°
After carrying out a heating reaction at an appropriate temperature range of ~160°C, adding dicarboxylic acids represented by the general formula (I[) or its dicarboxylic acid anhydride, and then heating reaction at an appropriate temperature of 150~250°C. It's okay.

After this reaction, to remove the target quinophthalone-based colored compound from the reaction mixture, cool the reaction mixture, separate the precipitate, and treat with dimethylformamide, dimethylacetamitometal, ethanol, or acetone. Just wash it.

Alternatively, the above-mentioned solvent may be added to the reaction mixture before the reaction mixture is cooled and treated.

If further purification is required, washing and recrystallization may be performed using a solvent such as dimethylformamide dimethylacetamide, N-methylpyrrolidone, α-chlormephthalene, or the like.

Alternatively, after cooling the reaction mixture, methanol, ethanol, dimethylformamide, etc. may be added to separate the precipitate.

The quinophthalone-based colored compound thus obtained can be further dissolved in concentrated sulfuric acid and converted into a pigment by a conventional pigment formation method such as reprecipitation.

As detailed above, according to the present invention, colored compounds of quinophthalone, which are novel compounds, can be easily produced, and these compounds have excellent heat resistance, light resistance, chemical resistance, and color tone. It can provide a compound useful as a coloring agent for printing inks, paints, and other polymeric materials, and its effectiveness is extremely impressive.

Next, examples will be shown.

"1 part" shown in the following examples is "part by weight."

Example 1 338 parts of 8-naphthaliminoquinaldine, 286 parts of tetrachlorophthalic anhydride, 40 parts of anhydrous zinc chloride, and 1.
2000 parts of 2,4-trichlorobenzene is reacted at the boiling point under subcurrent flow for 3 hours.

Next, 300 parts of dimethylformamide was added, and the mixture was stirred for an additional hour at the boiling point under a stationary flow.

After cooling, the yellow reaction product is washed with 1000 parts of dimethylformamide and finally with ethanol.

After drying, 472 parts of a yellow pigment represented by the following structural formula was obtained.

The melting point of this substance is 360°C or higher, and the visible spectrum has a maximum absorption near 444 mμ in dimethylformamide.

The elemental analysis values were as follows and almost agreed with the calculated values.

Example 2 338 parts of 8-naphthaliminoquinaldine, 464 parts of tetrafluorophthalic anhydride, 40 parts of anhydrous zinc chloride, ■・2・
2000 parts of 4-trichlorobenzene was reacted at the boiling point for 3 hours under reflux, then 300 parts of dimethylformamide was added and the mixture was further stirred at the boiling point for 1 hour under reflux.

After cooling, the yellow reaction product is washed with 1000 parts of dimethylformamide and finally with ethanol.

After drying, 588 parts of a yellow pigment represented by the following structural formula was obtained.

The melting point of this substance is 360°C or higher, and the visible spectrum has an extremely thick absorption near 447 mμ in dimethylformamide.

The elemental analysis values were as follows and almost agreed with the calculated values.

Example 3 8-(3-chlornaphthalimino)-quinarshif 373
parts, 286 parts of tetrachlorophthalic anhydride, 4 parts of anhydrous lead chloride
0 parts and 2000 parts of 1,2,4-trichlorobenzene were reacted for 3 hours under reflux at the boiling point, then 500 parts of dimethylformamide was added and the mixture was further stirred for 1 hour under reflux at the boiling point.

After cooling, the yellow reaction product is washed with 1000 parts of dimethylformamide and finally with ethanol.

After drying, 443 parts of a yellow pigment having the following structural formula was obtained.

The melting point of this substance is 360°C or higher, and the visible spectrum has an absorption around 444 mμ in dimethylformamide.

The elemental analysis values were as follows and almost agreed with the calculated values.

Example 4 8-(3-promnaphthalimino)-quinaldine 417
1, 286 parts of tetrachlorophthalic anhydride, 40 parts of anhydrous zinc chloride, and 2,000 parts of anhydrous zinc chloride were reacted under reflux at the boiling point for 3 hours, then 500 parts of dimethylformamide was added and stirred for an additional hour.

After cooling, the resulting yellow reaction product was washed with 1,000 parts of dimethylformamide and then with ethanol to obtain 449 parts of a yellow pigment having the following structural formula. The results of elemental analysis were as shown below, and almost agreed with the calculated values.

Example 5 A reaction was carried out in the same manner as in Example 3 using 373 parts of 8-(4-chlornaphthalimino)quinalshiff, 286 parts of tetrachlorophthalic anhydride, 40 parts of anhydrous zinc chloride, and 2000 parts of 2.2.4-trichlorobenzene. 421 parts of a yellow pigment having the following structural formula was obtained.

The melting point of this substance is 360°C or higher, and the visible spectrum has an extremely thick absorption near 444 mμ in dimethylformamide.

The elemental analysis results were as shown below and almost agreed with the calculated values.

Example 6 8-(3-fromnaphthalimino)-quinaldine 417
parts, 198 parts of naphthalic anhydride, 40 parts of anhydrous zinc chloride, ■
- 2000 parts of 2,4-trichlorobenzene are reacted at boiling point under reflux for 20 hours.

Next, 300 parts of dimethylformamide was added and the mixture was stirred for an additional hour under reflux at the boiling point.

After cooling and separation, the yellow reaction product obtained is washed with 1000 parts of dimethylformamide and then with ethanol.

After drying, 353 parts of a yellow pigment having the following structural formula was obtained.

The melting point of this substance is 360°C or higher, and the visible spectrum has a maximum absorption near 430 mμ in dimethylformamide.

The elemental analysis results were as shown below and almost agreed with the calculated values.

Example 7 7338 parts of 8-naphthaliminoquinaldi, 356 parts of 5,8-dibromo-2,3-naphthalene dicarboxylic acid, 40 parts of anhydrous zinc chloride, 20 parts of 1,2,4-trichlorobenzene
00 parts were reacted under reflux at the boiling point for 15 hours, then 300 parts of dimethylformamide was added and the mixture was further stirred at the boiling point for 1 hour under reflux.

After cooling, the resulting yellow reaction product was washed with 1000 parts of dimethylformamide and then with ethanol to obtain 570 parts of a yellow pigment having the following structural formula.

The melting point of this substance is 360°C or higher, and the visible spectrum has a maximum absorption near 459 mμ in dimethylformamide.

The elemental analysis results were as shown below and almost agreed with the calculated values.

Example 8 8-Naphthaliminoquinaldine 3 was prepared in the same manner as in Example 7.
38 parts, 4,5,6,7-titrabromo-2,3-naphthalene dicarboxylic acid 514 parts, anhydrous zinc chloride 40 parts, 1
- A yellow pigment having the following structural formula was obtained by reaction using 2,000 parts of 2,4-trichlorobenzene.

Example 9 Similar to Example 6, 8-(3-promnaphthalimino)-
A reaction was performed using 417 parts of quinaldine, 198 parts of 1,2-naphthalene dicarboxylic acid, 40 parts of anhydrous zinc chloride, and 2,000 parts of 1,2,4-trichlorobenzene to obtain a yellow pigment having the following structural formula.

Example IO 8-(tetrachlornaphthalimino) as in Example 6
-476 parts of quinaldine, 148 parts of phthalic anhydride, 40 parts of anhydrous zinc chloride, 2000 parts of 1,2,4-trichlorobenzene
A yellow pigment having the following structural formula was obtained.

Example 11 158 parts of 8-aminoquinaldine, 198 parts of naphthalic anhydride
1) 2000 parts of chlorobenzene at 160℃ for 6 hours
Stir with

Next, 572 parts of tetrachlorophthalic anhydride and 40 parts of anhydrous zinc chloride were added, and the mixture was reacted for 3 hours under reflux at the boiling point.

Next, 500 parts of dimethylformamide was added and the mixture was stirred for an additional hour under reflux at the boiling point.

After bow filtration at 150° C., the yellow reaction product was washed with 1000 parts of dimethylformamide and then with ethanol to obtain a yellow pigment similar to that obtained in Example 1.

Example 12 A product having the following structural formula in the same manner as in Example 7 except that 198 parts of 2,3-naphthalene dicarboxylic acid was used instead of 356 parts of 5,8-dibromo-2,3-naphthalene dicarboxylic acid. The compound was obtained.

Disperse 52 parts of the compound in 1000 parts of water, add 1 part of iodine, heat to 90-95°C, and dissolve bromine 64 while stirring uniformly.
of the mixture was added dropwise, and the reaction was further continued for 3 hours.

After cooling, it was separated and washed with methanol and water to obtain a product having the following structural formula into which two bromine atoms were introduced.

The melting point is 360°C or higher, and the visible spectrum has an absorption near 459 μm in dimethylformamide.

The elemental analysis value almost agreed with the value calculated assuming that two bromine atoms were introduced.

Claims (1)

[Claims] 1 The following general formula (I) [In the formula, A and B represent a benzene ring which may be substituted with a halogen atom. ] and the following general formula CII)
[In the formula, X represents a phenylene group or a naphthylene group, which may be substituted with a halogen atom, and in which two carbonyl groups are bonded at the ortho or peri position. ] The following general formula (I [[) [in the formula A, B
, X is as described above.] A method for producing a colored compound represented by: