JPS5851025B2 - Kinophthalonkeikagobutsunoseizouhouhou - 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 inventor has discovered that when a certain compound is reacted, the formula CII
I) [In the formula, ring A may be substituted with a halogen atom.

X represents a lower alkyl group, a phenyl group, or CONH2.

Z represents a phenylene group or a naphthylene group in which two carbonyl groups (carboxyl groups) are bonded at ortho positions, and may be substituted with a nonionizable substituent.

] was obtained, and the present invention was achieved 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 General formula below [■] (In the formula, A and X are as described above.

A quinoline derivative represented by General formula (n) below ) (In the formula, Z is as described above.

) or its carboxylic acid anhydride, and is further reacted with the following general formula Cm) (wherein A, X, and Z are as described above). .

) is a method for producing a colored compound represented by

The compound represented by the general formula [III] produced by the method of the present invention may form the following tautomeric structure, but in the method of the present invention, the compound represented by the general formula [■] can form all of these tautomeric structures. Structural formula, (IIIa), [■], [■b]
This includes:

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-phthalimide, 2,4-dimethylquinoline, 8-(tetrachlorophthalimide)-2,4-dimethylquinoline, 8-(tetrabromophthalimide)-2,4-dimethylquinoline, 8
-7thalimide 4-phenylquinaldine, 8-(tetrachlorophthalimide)-4-phenylquinaldine, 8
-(Tetrabromophthalimide)-4-phenylquinaldine, 8-phthalimido-quinaldine-4-carboxylic acid amide, 8-(tetrachlorophthalimide)quinaldine-4-carboxylic acid amide, 8-(tetrabromophthalimide)-quinaldine- There are many compounds such as 4-carboxylic acid amide.

These compounds are 8-amino-4-methylquinaldine,
It can be easily synthesized by heating and reacting 8-amino-4-phenylquinaldine, 8-aminoquinaldine-4-carboxylic acid amide, etc. with phthalic anhydride or its halogenated derivative.

8-Amino-4-methylquinaldine is synthesized by a known method.

8-Amino-4-phenylquinaldine is, for example, 1-phenylbutanol(3)one (1) obtained by condensing acetophenone and acetaldehyde, or 8-amino-4-phenylquinaldine obtained by condensing ethysodenacetophenone and 0-chloroaniline.
Chlor-4-phenylquinaldine can be produced by heating with aqueous ammonia under a copper catalyst.

In addition, 8-aminoquinaldine-4-carboxylic acid amide can be obtained by heating 8-chloroquinaldine-4-carboxylic acid amide obtained by reacting 7-chloroisatin with acetone and aqueous ammonia with aqueous ammonia in the presence of a copper catalyst. are synthesized.

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

The reaction of the method 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, examples of the solvent used include organic solvents inert to the reaction, such as nitrobenzene, orthodichlorobenzene, trichlorobenzene, trimethylbenzene, tecarin, tetralin, diphenyl ether, chlornaphthalene, and N-methylpyrrolidone. etc. are used.

The amount used may be 2 to 20 times the weight of the reactant, 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 acids or dicarboxylic acid anhydrides represented by the above formula [■] may be within any range, but the preferred ratio of both is 0.3. It may be in the range of ~3.

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, but in order to carry out the reaction more effectively, zinc chloride, aluminum chloride, or boron trifluoride ether complex can be used. This is done by adding a catalyst such as

When a catalyst is used, a lower reaction temperature range is used; when a catalyst is not used, a higher temperature range is used to obtain good results.

Further, in the present invention, a quinoline derivative represented by the general formula CI) is used as a raw material, but there is no need to isolate this raw material in advance, and the 8-aminoquinaldine derivative and phthalic anhydride or its halogenated derivative are mixed at 120% ~
After a heating reaction at an appropriate temperature of 260°C, the above general formula [
It may be produced by adding the dicarboxylic acids or dicarboxylic anhydrides shown in (2) and then heating the reaction mixture at a temperature of 150 to 27 oX'cnl.

Furthermore, the dicarboxylic acids represented by the general formula CII),
When using phthalic anhydride or its halogenated derivative to be reacted with the 8-aminoquinaldine derivative, add two or more equivalents of dicarboxylic acids to the 8-aminoquinaldine derivative from the beginning. You may react.

After this reaction, in order to remove the target colored quinophthalone compound from the reaction mixture, the reaction mixture is cooled, the precipitate that has separated out is separated, and the precipitate is washed with dimethylformamide, dimethylacetamide, methanol, ethanol, or acetone. Bye.

Alternatively, the above-mentioned solvent may be added 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-chlornaphthalene, 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 optionally 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 compounds useful as coloring agents for printing inks, paints, and other polymeric materials, and its effects are extremely large.

Next, examples will be shown.

"Parts" shown in the following examples are "parts by weight."

Example 1 440 parts of 8-(tetrachlorophthalimide)-2.4 dimethylquinoline, 286 parts of tetrachlorophthalic anhydride,
40 parts of anhydrous zinc chloride and 1200 parts of 1,2,4-trichlorobenzene are reacted at boiling point under reflux for 3 hours.

Next, 300 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, 552 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.

Analysis value: C, 45,95; H, 1,04; N13,78
;C1゜39.60%, calculated value: C145,81;H
ll, 14; N, 3.96; C1, 40,06% Example 2 172 parts of 8-amino-2,4-dimethylquinoline and 572 parts of tetrachlorophthalic anhydride were mixed with 1 part of diphenyl ether.
The mixture was reacted for 4 hours under reflux in 200 parts of the mixture, cooled, separated, and the yellow reaction product was washed with dimethylformamide.

After drying, 560 parts of yellow pigment were obtained.

The infrared absorption spectrum completely matched that of the pigment obtained by the method of Example 1.

Example 3 440 parts of 8-(tetrachlorophthalimide)-2,4-dimethylquinoline, 464 parts of tetrafrom phthalic anhydride, 40 parts of anhydrous zinc chloride, and 2000 parts of 1,2,4-trichlorobenzene were refluxed at the boiling point. After reacting for 3 hours, 300 parts of dimethylformamide was added and the mixture was further stirred for 1 hour under reflux at the boiling point.

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

After drying, 664 parts of a yellow pigment represented by the following structural formula was obtained.

The melting point of this substance was 360°C or higher, and the visible spectrum showed a maximum absorption near 444 mμ off the coast of dimethylformamide.

Elemental analysis values are C, 36,83; H, 0,75; N13.
02; Calculated value C136,59 with halogen 51.86%
;H.

0.90; N, 3.16; halogen 52.12
% was almost the same.

Example 4 440 parts of 8-(tetrachlorophthalimide)-2,4 dimethylquinoline, 514 parts of 5,6,7,8-tetrabromnaphthalene 2,3-dicarboxylic anhydride, 40 parts of anhydrous zinc chloride, and 1,2・4-Trichlorobenzene 200
0 part was reacted under reflux at the boiling point for 3 hours, 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 was separated and washed with 1000 parts of dimethylformamide, and finally washed with ethanol and dried to obtain 730 parts of a yellow pigment having the following structural formula.

The melting point of this substance is over 360°C, and the visible spectrum shows an absorption near 444 mμ in dimethylformamide.The elemental analysis values are C139,56; Hll, 12; N, 2.87
; Calculated value C139.78 at No. 49.02%; H
ll, 08; N, 2.99; almost matched with halogen 49.31%.

Example 5 302 parts of 8-phthalimido-2,4-dimethylquinoline, 286 parts of tetrachlorophthalic anhydride, 4 parts of anhydrous zinc chloride
0 parts, 2000 parts of 1,2,4-trichlorobenzene were reacted under reflux at the boiling point for 3 hours, then 500 parts of dimethylformamide was added and the mixture was further stirred for 1 hour.

After cooling, the obtained yellow reaction product was washed with 1000 parts of dimethylformamide and then with ethanol to obtain 428 parts of a yellow pigment having the following structural formula.

The melting point of this substance is over 360℃ and the visible spectrum is 44.
The elemental analysis value with maximum absorption near 4 mμ is C156,6
7; H, 2,08; N, 4.85; C1,24,6
Calculated value at 4% C, 56, 87H, 2, 12; N, 4
．． 91; almost identical to C1, 24.87%.

Example 6 8-(tetrachlorophthalimide)-quinaldine-4-
469 parts of carboxylic acid amide, 286 parts of tetrachlorophthalic anhydride, 40 parts of anhydrous zinc chloride and 2000 parts of trichlorobenzene are reacted under reflux at the boiling point for 3 hours, then 300 parts of dimethylformamide is added and stirred for an additional hour.

After cooling, the resulting yellow reaction product was washed with 1000 parts of dimethylformamide and then with ethanol to obtain 553 parts of a yellow pigment having the following structure.

The melting point of this substance is over 360℃ and the visible spectrum is 44.
The elemental analysis value is C144, which shows maximum absorption near 4 mμ.
12; H, 0.90; N, 5.75; C1.

Calculated value at 38.25% C, 44,00; H, 0,96;
N, 5.70; almost identical to C1, 38.49%.

Example 7 502 parts of 8-(tetrachlorophthalimide)-4-phenylquinaldine and 286 parts of tetrachlorophthalic anhydride were added to 2000 parts of trichlorobenzene together with 40 parts of zinc chloride and reacted under reflux at the boiling point for 3 hours, and then 300 parts of dimethylformamide was added. 1 part was added and the mixture was further refluxed for 1 hour.

After cooling, the yellow reaction product obtained was mixed with dimethylformamide.

1 part, and then washed with ethanol and dried to obtain 578 parts of a yellow pigment having the following structure.

The melting point of this substance is over 360℃ and the visible spectrum is 44.
The elemental analysis value with maximum absorption near 4 mμ is C149.7
5; H, 1, 12; N, 3.75; C1, 36,
Calculated value at 38% C, 49, 91; Hll, 31; N1
3.64; almost identical to C1136, 83%.

Example 8 502 parts of 8-(tetrachlorophthalimide)-4-phenylquinaldine and 464 parts of tetrabromophthalic anhydride,
40 parts of anhydrous zinc chloride and 2000 parts of trichlorobenzene were reacted for 3 hours under reflux at the boiling point, then 300 parts of dimethylformamide was added and stirred for an additional 1 hour under reflux at the boiling point.

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

After drying, 739 parts of a yellow pigment represented by the following structural formula was obtained.

The melting point of this product was 360°C or higher.

Elemental analysis values are C140, 22; Hll, 15; N. 2.
78; Calculated value C140.54 at halogen, 48.23%
;H, 1,06;N12.96 ;Halogen 48.68
% was almost the same.

Example (tetrachlorophthalimide) 502 parts of phenylquinaldine, 514 parts of 5,6,7,8-tetrabromnaphthalene-2,3-dicarboxylic anhydride,
40 parts of anhydrous zinc chloride and 2000 parts of trichlorobenzene
1 part was reacted under reflux at the boiling point for 3 hours, then 500 parts of dimethylformamide was added and stirred for an additional hour under reflux at the boiling point.

After cooling, the yellow reaction product was separated and washed with 1000 parts of dimethylformamide, and finally washed with ethanol and dried to obtain 768 parts of a yellow pigment having the following structural formula.

The melting point is over 360℃ and the elemental analysis value is C143,15;H
, 1,08; N, 2.77; Halogen 46.02%
Then, the calculated values are C, 43, 32; Hll, 21; N, 2.
81; Almost identical to 46.24% halogen.

Claims (1)

[Claims] 1 The following general formula CI) [In the formula, ring A may be substituted with a rogen atom. X represents a lower alkyl group, a phenyl group, or CONH2. ] A quinoline derivative represented by the following general formula [■] [In the formula, 2 represents a phenylene group or a naphthylene group in which two carbonyl groups (carboxyl groups) are bonded at the ortho position, and is substituted with a halogen atom. It's okay. ] The following general formula [■] (wherein A, X, Z
is as described above) A method for producing a quinophthalone compound represented by: