JPS5855186B2 - Manufacturing method of pigment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel pigment derived from pyridine-carboxylic acid, which is essentially colorless and can develop color upon contact with an acidic substance. .

More specifically, the present invention relates to the following general formula (wherein R4 represents a hydrogen atom, a lower alkyl group, or an optionally substituted benzyl group, and R2 represents a lower alkyl group, an optionally substituted benzyl group, or a phenyl group). , R3 represents a hydrogen atom, a lower alkyl group, a halogen atom or a phenyl group, R4 represents a hydrogen atom, a lower alkyl group, an optionally substituted benzyl group or a phenyl group, and R5 represents a hydrogen atom, a lower alkyl group ,
It represents an optionally substituted benzyl group or acyl group, and R6 represents a hydrogen atom, a lower alkyl group or a halogen atom.

) The present invention relates to a method for producing a novel dye derived from pyridinecarboxylic acid, represented by:

Traditionally, such pigments include crystal violet lactone, malachite green lactone, rhodamine lactam derivatives, leuco auramine derivatives, leuco methylene blue derivatives, indolinospiropyran derivatives, and leuco lactones of bis(P-substituted aminoaryl)-methane.
Derivatives such as auramine compounds or their quaternized products or sulfonated products are known.

However, these have slow color development speed, low color density, low light fastness and weather resistance of the pigment produced by color development, and the color tone changes over time. Also, the color may bleed or develop during storage. , or has drawbacks such as a decrease in coloring performance.

The object of the present invention is to be stable during storage, not to easily decompose or develop color even when exposed to direct sunlight, water, oxygen, etc., and to rapidly develop a deep color when heated or in contact with acidic substances. The object of the present invention is to provide a method for producing an essentially colorless dye in which the resulting dye has excellent light resistance and weather resistance.

In the method of the present invention, the general formula (wherein R represents a hydrogen atom or a lower alkyl group, R
1 represents a hydrogen atom, a lower alkyl group, or an optionally substituted benzyl group, R2 represents a lower alkyl group, an optionally substituted benzyl group, or a phenyl group, and R3 represents a hydrogen atom, a lower alkyl group, a halogen atom, or Represents a phenyl group.

) and a benzoyl-pyridine-carboxylic oxidation product represented by the general formula (wherein R4 represents a hydrogen atom, a lower alkyl group, an optionally substituted benzyl group or a phenyl group, and R5 represents a hydrogen atom, a lower alkyl group, represents a benzyl group or acyl group substituted with 5 3rd or 4th place.

) is condensed with an aniline compound represented by the general formula (wherein R1, R2, R3, R4, R5 and R6 have the same meanings as defined above).

) A novel pyridine-carboxylic acid lactone dye is prepared.

The method of the present invention can also be carried out by the following method, that is, the above-mentioned production method, by producing a compound of the general formula (wherein R1, R2, R3, R4 and R6 have the same meanings as defined above).

) is produced, and this compound and the general formula (V) R5-Y (V) (in the formula R5
has the same meaning as defined above, except when it is a hydrogen atom, and Y represents a residue of a lower alkylating agent, benzylating agent, or acylating agent.

) is condensed with a lower alkylating agent, benzylating agent or acylating agent represented by the general formula (wherein R1, R2, R3, R4, R5 and R6 have the same meanings as defined above).

It also includes a method for producing a novel pyridine-carboxylic acid lactone dye represented by:

The novel pigments obtained by the process of the invention are essentially colorless or slightly colored powders.

This powder is stable in the air, but when heated, it changes color from colorless or faintly colored to red, reddish-brown, dark reddish-brown, dark blue, blue-black, or green-black.

It can also be dissolved or mixed in high molecular compounds such as animal, vegetable or mineral waxes, ethyl cellulose, polyvinyl acetate, rosin modified alkyd resins and the like.

The novel dye is also soluble in a wide range of organic liquids such as methanol, ethanol, ethyl cellosolve, chloroform, benzene-toluene, benzene chloride, alkylnaphthalenes, benzyltoluene, dibenzyltoluene, dibenzylbenzene or trioctylphosphate. activated clay materials such as acid clay, acpargide, theolite or bentonite or trisuccinic acid,
It immediately adsorbs to organic solid acids such as maleic acid, tannic acid, and benzoic acid, or acidic polymers such as carboxypolyethylene, phenol-aldehyde polymers, and styrene-maleic anhydride copolymers with residual acidic groups. It develops colors such as red, reddish-brown, dark reddish-brown, dark blue, blue-black, or green-black, and its color density is high, and the developed pigment has excellent water resistance and light resistance. It has great utility as a marking pigment for recording materials such as thermal copying paper, hectograph transfer paper, and pressure-sensitive copying paper.

Representative compounds of the benzoyl-pyridine-carboxylic acid represented by the general formula [formerly 2-[2-hydroxy 4-diethylamino-
Benzoylcopyridinecarboxylic acid-(3); 2-(2-
Methoxy-4-dimethylamino-benzoylcopyridine-carboxylic acid (8); 2-(2-ethoxy-4-diethylaminobenzoylcopyridine-carboxylic acid-(3);
2[2-methoxy-4-(N-methyl-N-benzyl)
Amino-benzoylcopyridine-carboxylic acid (8); 2
-(2-methoxy-4-dibenzylamino-benzoylcopyridine-carboxylic acid-(3); 2[2-hydroxy-4-benzylamino-benzoylcopyridine-carboxylic acid-(3); 2-(2hydroxy -4-anilino-benzoylcopyridine-carboxylic acid-13); 2-(2
-methoxy-4(N-methyl-N-phenyl)aminobenzuyl]pyridine-carboxylic acid-(3); 2-[2
-hydroxy-4-para-toluidino-benzoylcopyridine-carboxylic acid-(3); 2-(2-hydroxy4
-(4-chloroanilino)-benzoylcopyridine-carboxylic acid-(8); 2-(2-methoxy4-cy(4)
-'70 rubenzyl)amino-benzoylcopyridine-
Carboxylic acid-(8); 2-(2-methoxy-4-di(
4-Methylbenzyl)aminobenzoylcopyridine-carboxylic acid-(3); 2[2-methoxy-4-di(4-
dimethylaminobenzyl)amino-benzoylcopyridine-carboxylic acid-3); 2-(2-ethoxy-4-diethylamino-benzoyl]-4-methyl-pyridinecarboxylic acid-(8); 2-(2-ethoxy- 4-diethylamino-benzoyl-4-chloro-pyridine-carboxylic acid-(8); 2-(2-ethoxy-4-diethylamino-benzoyl-6-phenylpyridine-carboxylic acid-
(8); 2-(2-oxy4-dibutylamino-benzoylcopyridine-carboxylic acid-(3)) and the like.

Further, the general formula (II) used in the method of the present invention
Representative aniline compounds represented by I) include 4-amino-phenol; para-anisidine: para-phenetidine; 3-methyl-4-amino-phenol;
3,4-dimethoxy-aniline: 4-methylamino-phenol; 3-chloro-4-ethylamino-phenol; 4-butylamino-phenol; 4-diethylamino-phenol; 3-chloro-4-diethylamino-phenol; 3 -dimethylamino-phenol; 3ethylamino-phenol: 3-diethylamino-4-chloro-
Phenol; 4-benzylamino-phenol; 4-(
N-ethyl-N-benzyl)amino-phenol; 4-
Dibenzylamino-phenol; 3-Methyl-4-dibenzylamino-phenol; 3-chloro-4-dibenzylamino-phenol; 3-ethyl-4-dibenzylamino-phenol; 4-di(4-methylbenzyl ) Amino-phenol; 4-dibenzylamino-anisole; 4-di(4-chlorobenzyl)amino-anisole; 3-dibenzylamino-phenol; 4-hydroxy-diphenylamine; 4-hydroxy-47-methyl-
Diphenylamine; 4-hydroxy-37-methyl-diphenylamine; 4-hydroxy-27-methyl-diphenylamine; 4-hydroxy-27,4/-dimethyl-diphenylamine; 4-hydroxy-2'-carboxydiphenylamine; 2-methyl-4 -hydroxy-diphenylamine; 2,4'-dimethyl-4hydroxy-diphenylamine: 2-methyl-4hydroxy-2
'-Carboxy-diphenylamine; 2-methyl-4-
Hydroxy-47-chlordiphenylamine; 2,
4'-dimethoxy-diphenylamine;4,4'-
Dimethoxy-diphenylamine; 4-methoxy-47-
Dimethylaminodiphenylamine; 4,4'-';
Ethoxydiphenylamine; 4-methoxy-2'-ethoxycarbonyldiphenylamine; N-methyl-4-
Hydroxy-diphenylamine; N-butyl-4-hydroxy-diphenylamine; N-benzyl-4-hydroxy-diphenylamine; N-methyl-4methoxy-diphenylamine; N-methyl-4°4'-dimethoxy-
Diphenylamine; 3-hydroxy-diphenylamine; 4-acetamido-phenol; 4-propionamide-phenol; 4-benzamide-phenol; 4-
(N-methyl-N-4-chlorobenzoyl)amino-anisole and the like.

The benzoyl-pyridine-carboxylic acid represented by the general formula [formula] is generally produced by the following methods (1) to (4).

(1) Quinolinic anhydride and an aniline compound corresponding to benzoyl-pyridine-carboxylic acid represented by the general formula The reaction is carried out in an inert solvent using a Friedel-Crafts catalyst such as zinc chloride, phosphorous chloride or aluminum chloride at a temperature of 10-110° C. for 1-9 hours.

(2) Quinolinic anhydride and an aniline compound corresponding to benzoyl-pyridine-carboxylic acid represented by the general formula Allow to react for 2 to 8 hours.

(3) Quinolinic anhydride and the aniline compound corresponding to the benzoyl-pyridine-carboxylic acid represented by the general formula CII) are mixed together at a temperature of 100-180°C for 2 to 10 minutes with or without the above organic inert solvent. Allow time to react.

(4) Quinolinic acid is reacted with sulfuryl chloride or phosphorus pentachloride to produce quinolinic acid chloride, and this chloride is mixed with the above-mentioned organic inorganic compound corresponding to benzoyl-pyridine-carboxylic acid represented by the general formula (ID). The reaction is carried out using a Friedel-Crafts catalyst in an active solvent.

Among the above manufacturing methods, method (1) is particularly desirable.

Here, the manufacturing method (1) will be explained in more detail.

1.0 mol of quinolinic anhydride, 0.9 to 2.0 mol, preferably 1.0 to 1.5 mol, of an aniline compound corresponding to benzoyl-pyridine-carboxylic acid represented by the general formula Kraft catalyst 1.0-3.0
mol, preferably from 1.0 to 1.5 mol, is added into the volatile organic inert solvent from 0.5 to 2.51, and from 10 to 1100
The reaction is carried out at a temperature of C for 1 to 9 hours.

After cooling to room temperature, by the following method (1) or (2), 2-benzoylpyridine-carboxylic acid-(3) and 3-benzoylpyridine-carboxylic acid-(2) represented by the general formula A mixture of crystalline isomers is obtained.

(1) The reaction product obtained by removing the organic inert solvent by decanting is added to 2-61 ice water or cold dilute hydrochloric acid solution, the catalyst is hydrolyzed, the precipitated solid is separated, washed with water, and then Method: Wash with alcohol or benzene and dry.

(2) Add to ice water of 2 to 61 and hydrolyze the catalyst,
Subsequently, the organic inert solvent is forcefully applied, the reaction product is transferred to the solvent layer, the solvent layer is separated, and the solvent is distilled off.

In addition, the above isomer mixture is treated with high purity 3-benzoyl-pyridine by any of the methods (1) to (3) below.
Carboxylic acid = (2) and 2-benzoyl-pyridine-
The carboxylic acid-(3) is obtained in separate crystals.

(1) Add and dissolve in dilute sodium hydroxide water, add dilute hydrochloric acid water little by little to this solution, and separate the solid that precipitates due to the difference in pH of the solution.

(2) Recrystallization several times from a mixed solvent consisting of a less polar solvent such as benzene or toluene and a more polar solvent such as methanol or butanol.

(3) Use methods (1) and (2) above together.

In the present invention, the lactone compound of pyridine-carboxylic acid represented by the general formula [I] is combined with the benzoyl-pyridine-carboxylic acid represented by the general formula [old] and the general formula Cl
It is produced by reacting an aniline compound represented by 10 in the presence of a condensing agent.

To facilitate the condensation reaction, a volatile organic inert liquid such as chloroform, tetrachloroethane, benzene or benzene chloride may be used as a solvent, if necessary.

Condensing agents that can be used include concentrated sulfuric acid, oleum, acetic anhydride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, phosphoric acid, polyphosphoric acid, zinc chloride, stannic chloride, and aluminum chloride.

However, it is even more desirable to use concentrated sulfuric acid, fuming sulfuric acid or polyphosphoric acid, which are both condensing agents and solvents for the reaction.

This manufacturing method will be explained in more detail.

That is, 10 moles of the benzoyl-pyridine-carboxylic acid represented by the general formula [old] and the aniline compound represented by the general formula (1) 1. O to 2.0 mol, preferably 1.0 mol.
O-1.5 mol and diluted with concentrated sulfuric acid, fuming sulfuric acid or poIJI
After adding the reaction product into a 3-30 cell of J.
dilute the condensing agent in ice water, then add dilute hydroxide solution.
- Adjust the pH to 11-12 by adding IJum water, separate the precipitated solids, wash with water, wash with a small amount of petroleum ether or alcohol, and dry. A pyridine-carboxylic acid lactone dye represented by the general formula (1) is obtained.

Alternatively, add dilute sodium hydroxide solution to adjust the pH.
After adjusting the amount to 11 to 12, benzene or toluene is added and stirred to transfer the pyridine-carboxylic acid lactone dye to the benzene or toluene layer, and the benzene or toluene layer is separated.

When the residue obtained by distilling off benzene or toluene from this fractionated benzene or toluene layer is washed with water, washed with a small amount of petroleum ether or alcohol, and dried, it is mostly colorless or slightly colored. General formula C
A lactone dye of pyridine-carboxylic acid represented by I] is obtained.

If necessary, the resulting pyridine-carboxylic acid lactone dye is recrystallized from a suitable solvent.

Among the dyes obtained by the method of the present invention, general formula CIV
) is the lactone of 2-[3-diethylamino-7-amino-9-oxy-xanthylkopyridine-carboxylic acid-(3);
Lactone of diethylamine-6-methyl-7-amino-9-oxy-xanthylkopyridine-carboxylic acid-(3); 2-(3-'; ethylamino-5-methoxy-7-
Lactone of amino-9-oxy-xanthylkopyridine-carboxylic acid (8); 2-(3-(N-methyl-N-
lactone of phenyl)amino-7-amino-9-oxy-xanthylkopyridine-carboxylic acid-(3);
-diethylamine-7-methylamino-9oxy-xanthylkopyridine-lactone of carboxylic acid (3); 2-
(3-dimethylamino-6chloro-7-ethylamino-9-oxy-xanthylkopyridine-carboxylic acid-(3
) lactone of 2[3-diethylamino-7-pendylamino 9-oxy-xanthylkopyridine-carboxylic acid (3); 2-(3-diethylamine-7(4
-Chlorbenzyl)amino-9-oxyxanthylkopyridine-carboxylic acid-(3) lactone; 2-(3-diethylamino-7-anilino-9-oxy-xanthylkopyridine-carboxylic acid-(3) lactone; 2-[3
lactone of -diethylamino-6-methyl-7-anilino-9-oxy-xanthylkopyridine-carboxylic acid-(3); 2[3-diethylamino-6-methyl-7-(2
lactone of 2-(3-diethylamino-7-para-toluidino-9oxy-xanthylkopyridine-carboxylic acid-(3)); 2-(
Lactone of 3,7-dianilino-9-oxyxanthyl]pyridine-carbone-(3); Lactone of 2-[3-diethylamino-7-penzamido-9-oxy-xanthylkopyridinecarboxylic acid-(3); 2 -[3-
Lactone of dibenzylamino-7-penzamido-9-oxy-xanthylkopyridine-carboxylic acid (3):
Lactone of 2-[3-diethylamino-7-acetamido-9-oxy-xanthylkopyridine-carboxylic acid (3);
(3) lactone; 2[3-diethylamine-7-amino-9-oxy-xanthyl-4-chloro-pyridine-carboxylic acid-(3) lactone; and 2-[3-diethylamino-7-amino-9- Oxyxanal]
Examples include lactone of 6-phenyl-pyridine-carboxylic acid (3).

In addition, typical compounds of the alkylating agent, acylating agent, or benzylating agent represented by the general formula (V) include acetic anhydride; propionic anhydride; butyric anhydride; acrylic anhydride; crotonic anhydride; cinnamic anhydride benzoic anhydride; acetyl chloride; propionyl chloride; acroyl chloride; cinnamoyl chloride; acetyl bromide: benzoyl chloride; 4-chlorobenzoyl chloride; 3-nitropensoyl chloride; 2--i lombenzoyl chloride; 4-methylbenzoyl Chloride; 4-methoxybenzoyl chloride; 2,4-dimethoxy-benzoyl chloride; 3,4,5-trimethoxybenzoyl chloride; Benzoyl bromide: dimethyl sulfate; diethyl sulfate; menal para-toluenesulfonate; ethyl para-toluenesulfonate : trimethyl phosphoric acid; triethyl phosphoric acid: methyl chloride: ethyl bromide: butyl bromide; methyl iodide; benzyl chloride; 4-nitrobenzyl chloride: 4-chlorobenzyl chloride; 4-methylbenzyl chloride and 4-methoxybenzyl bromide and so on.

The pyridine-carboxylic acid lactone dye represented by the general formula CI, ) in the present invention can also be produced by the following method.

A lactone compound of pyridine-carboxylic acid represented by the general formula (IV) and an alkylating agent, acylating agent, or benzylating agent represented by the general formula (V, 1) are combined, if necessary, with water, chloroform, benzene, Using volatile organic inert solvents such as toluene, benzene chloride, and if necessary triethylamine, pyridine, dimethylaniline,
It is produced using an acid acceptor that is a volatile organic or water-soluble inorganic basic compound such as sulfur bicarbonate, sulfur carbonate, sulfur hydroxide, and potassium hydroxide.

More specifically, it is produced by the following methods (1) to (3).

(1) Add 1.0 mol of a pyridine-carboxylic acid lactone compound represented by general formula (IV) to 5 to 30 mol of the alkylating agent, acylating agent, or benzylating agent and add 4
React at a temperature of 0 to 130°C for 2 to 8 hours, cool to room temperature, add cold sodium hydroxide solution to completely decompose the alkylating agent, acylating agent, or benzylating agent, and then adjust the pH to 11 to 12. After that, the precipitated solid is sorted out, washed with water, washed with a small amount of petroleum ether or alcohol, and dried. A carboxylic acid lactone dye is obtained.

Alternatively, after adjusting the pH to 11-12, add chloroform or toluene and stir to transfer the lactone dye of pyridine-carboxylic acid to the chloroform or toluene layer, separate the chloroform or toluene layer, and separate the separated chloroform or toluene layer. Chloroform or toluene is distilled off from the toluene layer, and the residue is washed with a small amount of petroleum ether or alcohol and dried. A carboxylic acid lactone dye is obtained.

(2) Add 10 moles of a pyridine-carboxylic acid lactone compound represented by general formula (IV) to a mixed solution of 1 to 41 moles of water and 1.0 to 30 moles of the above volatile organic or water-soluble inorganic basic compound. , an alkylating agent, acylating agent or benzylating agent 1 represented by the general formula [V] is added to this solution.
．． 0-3. Add Q mol and heat at a temperature of 40 to 100°C for 2 to
After reacting for 8 hours, cooling to room temperature, adding sodium hydroxide water to adjust the pH to 11-12, and treating in the same manner as in (1) above, the mixture is almost colorless or slightly colored. A colored pyridine-carboxylic acid lactone dye represented by the general formula [1] is obtained.

(3) 1.0 mol of a lactone compound of pyridine-carboxylic acid represented by general formula (IV) is mixed with 1.0 to 5.51 mol of the above volatile organic inert solvent and the above volatile organic basic compound 1.
．． 0 to 3.0 mol or 1.0 mol of water-soluble inorganic basic compound
~3.0 mol of an aqueous solution and 1.0 to 3.0 mol of an alkylating agent, acylating agent, or benzylating agent represented by the general formula [■] to this solution, and 40 ~ 1
React at a temperature of 10°C for 2 to 8 hours, cool to room temperature,
After washing with water, the volatile organic inert solvent is distilled off, and the residue is washed with a small amount of petroleum ether or alcohol and dried. A lactone dye of pyridine-carboxylic acid is obtained.

The present invention will be explained below with reference to Examples.

Example 1 11 quinolinic anhydride and 26.9 yd of N,N-diethyl m-phenetidine were added to 100 yd of benzene, and 27 g of anhydrous aluminum chloride was added in small portions over a period of about 20 minutes at a temperature of 30-35°C while stirring. .

After the addition was completed, the reaction was carried out for 4 hours at a temperature of 35-38°C, then cooled to room temperature and benzene was removed by decanting.

The obtained reaction product was added to 300 ml of ice water and stirred.

The precipitated solid is separated daily, washed with water, and dried to form 3-[
2-ethoxy-4-diethylamino-benzoylcopyridine-carboxylic acid-(2) and 2-[2-ethoxy-4-
Diethylamino-benzoylcopyridine-carboxylic acid-
Isomer mixture with (3) 15. ! 11 was obtained as pale brown crystals.

The melting point of this crystal was 245-253°C.

Further, 15.5 g of this crystal was added and dissolved in dilute sodium hydroxide water.

Dilute hydrochloric acid water was added to this solution to adjust the pH of the solution to 6, and the precipitated solid was separated, washed with water, and dried to give 3-[2
-Ethoxy-4-diethylamino-benzoylcopyridine-carboxylic acid-(2) is the main component, and 2-[2-
Ethoxy4-dienalaminobenzoyl]pyridine-
Isomer mixture 1 containing a small amount of carboxylic acid-(3)
0 g was obtained as light tan crystals.

The melting point of this crystal was 293-297°C.

10 g of this crystal was recrystallized several times from a mixed solvent of methanol and benzene to obtain 3-[2-ethoxy-4-diethylamino-benzoylcopyridine-rulfo7e-(2),
6.5 g was obtained as pale yellow, highly pure crystals.

The melting point of this crystal was 297-298°C.

On the other hand, diluted hydrochloric acid water was added to the pH 6 oral solution from which the above solids had been removed, the pH of the solution was adjusted to 2, and the precipitated solids were removed, washed with water, and dried. Diethylamino-benzoylcopyridine-carboxylic acid-(3
) is the main component, and an isomer mixture 4.0. ! ;' was obtained as pale brown crystals.

The melting point of this crystal was 176-181°C.

When this crystal 4.1 was recrystallized several times from a mixed solvent of methanol and toluene, 2-[2-ethoxy-4diethylamino-benzoylcopyridine-carboxylic acid-(3), 2
．． 3 g was obtained as almost colorless, highly pure crystals.

The melting point of this crystal was 179-180°C.

2-[2-ethoxy-4 with the above melting point of 179 to iso'c
-diethylamino-benzoylcopyridinecarboxylic acid-
(3) 2.0 g and 0.9 4-amino-phenol
,? was added to 7 g of 95% sulfuric acid, reacted at a temperature of 95 to 100°C for 6 hours, and then cooled to room temperature.

The reaction product was placed in ice water (60°C), and while stirring, diluted sodium hydroxide was added to adjust the pH of the aqueous solution to approximately 11.
50rrLl of benzene was added to this, the lactone of pyridine-carboxylic acid was transferred to the benzene layer, and the benzene layer was collected by liquid separation.

The residue obtained by distilling off benzene from this benzene layer is washed with water, washed with a small amount of petroleum ether, and then dried. It is colored pale pink.2-[3-
0.8 g of the lactone of diethylamino-7-amino-9-oxy-xanthyrcopyridine-carbon I-(3) was obtained in the form of crystals.

The melting point of this crystal was 168-172°C.

A benzene solution of these crystals was adsorbed on acid clay and immediately developed a dark reddish-brown color.

Example 2 2-(2-
Take 3.4 g of ethoxy-4-dienalaminobenzoyl)pyridine-carboxylic acid (3) and one of the 13 types of aniline compounds listed in Table 1 in the amounts shown in Table 1, and add them. Add to 12g of 95% sulfuric acid and add 95 to 100
The reaction was carried out at a temperature of 0C for 8 hours.

After the reaction, the following lactone was obtained by processing in the same manner as in Example 1.

[ ] represents the abbreviation of lactone.

[Ban, 2-a:] 2-[3-diethylamino-6-methyl-7-amino-
9-oxy-xanthylkopyridine-carboxylic acid-(3
) lactones.

[A2-b] 2-[3-diethylamino-6-amino-9-oxy-
Lactone of xanthyrcopyridine-carboxylic acid-(3).

[Arashi 2-c] Lactone of 2-[3-diethylamino-7-methylamino 9-oxy-xanthylkopyridine-carboxylic acid-(3).

[&2-d] Lactone of 2-(3,7-bis-diethylamino-9-oxy-xanthylkopyridine-carboxylic acid-(3).

(A2 e'J 2-(3-diethylamino-7-pendylamino-9-
Lactone of oxy-xanthyrcopyridine-carboxylic acid-(3).

(A2f) Lactone of 2-[3-diethylamino-6-chloro-7-dibenzylamino-9-oxy-xananarcopyridine-carboxylic acid-(3).

(A2 g) 2-[3-diethylamino-7-anilino-9oxy-
Lactone of xanthyrcopyridine-carboxylic acid (3).

(A2-h) 2-[3-diethylamino-6-methyl-7-anilino-9-oxy-xanthircopyridine-carboxylic acid-(
3) Lactone.

[, 柘2-1] Lactone of 2-[3-diethylamino-6-methyl-7-(2-carboxyanilino)-9-oxy-xanthylkopyridine-carboxylic acid-(3).

[Gan 2-J] 2-[3-diethylamino-7-P-4 luidino 9-
Lactone of oxy-xanthyrcopyridine-carboxylic acid-(3).

[A2-k] Lactone of 2-[3-diethylamino-7-(N-methylN-phenyl)amino-9-oxy-xanthylkopyridine-carboxylic acid-(3).

[A2-1] Lactone of 2-(3-diethylamino-7-penzamide 9-oxy-xanthyrcopyridine-carboxylic acid-(3).

(A2-m) 2-(3-diethylamino-6-propionamide-9
-Oxy-xanthircopyridine-carboxylic acid-(3)
lactone.

Example 3 7.0 g of quinolinic anhydride and 14.1 g of N-methyl-Nphenyl-m-anisidine are added to 80 g of benzene,
18.8 g of anhydrous aluminum chloride was added over 20 minutes at a temperature of 20-34° C. while stirring.

After the addition was completed, the reaction was carried out for 4 hours at a temperature of 45 to 50°C.
Cool to room temperature and remove benzene by decanting.

The reaction product was added to 300 ml of ice water and stirred.

The precipitated solid was separated, washed with water, and dried to give a light brown colored 3[2-methoxy-4-(N-methyl-
N-phenyl)amino-benzoylcopyridine-carboxylic acid (2) and 2-[2-methoxy-4-(N-methylN
13.6 g of an isomer mixture with -phenyl)amino-benzoylcopyridinecarboxylic acid (3) were obtained in the form of crystals.

The melting point of this crystal was 205-217°C.

This isomer mixture was prepared by the method described in Example 1.
[2-methoxy-4-(N-methyl-N-phenyl)amino-benzoylcopyridine-carboxylic acid-(2) and 2
-[2-methoxy-4(N-meth-N-phenyl]aminobenzoyl]pyridine-carboxylic acid-(3).

The above 2-[2-methoxy-4-(N-methylN-phenyl)aminobenzoyl]pyridine-carboxylic acid-(3)
3.6.9 and 1.4 g of 4-amino-phenol at 20
% fuming sulfuric acid and at a temperature of 70 to 80°C.
After reacting for an hour, the mixture was cooled to room temperature.

The reaction product was placed in 100 d of ice water, and while stirring, diluted sodium hydroxide was added to adjust the pH of the aqueous solution to approximately 12. Then, 80 yd of benzene was added to transfer the pyridine-carboxylic acid lactone to the benzene layer. was collected by liquid separation.

Benzene is distilled off from this benzene layer, and the resulting residue is washed with water, washed with a small amount of petroleum ether, and then dried.
2-(3-(
N-methyl-N-phenyl)amino-7-amino-9-
0.5 g of lactone of oxy-xanthyrcopyridine-carboxylic acid-(3) was obtained in the form of crystals.

A benzene solution of these crystals was adsorbed on acid clay and immediately developed a dark reddish-brown color.

Example 4 2-[2-methoxy-4-(N-methyl-N-phenyl)aminobenzoylcopyridine-carboxylic acid-(3) 3.6.9 and N-methyl 4-hydroxy described in Example 3 - Diphenylamine 2.1.1 in 20% oleum 1O
g and reacted at a temperature of 70 to 80°C for 5 hours.

After the reaction, the same method as in Example 3 was carried out to obtain 2-[3,7-bis=(N
-Methyl N-phenyl)amino-9-oxy-xanthylkopyridine-carboxylic acid-(3) lactone 0.7 g
was obtained as a crystal.

A toluene solution of these crystals was adsorbed on acid clay and immediately developed a blue-black color.

Example 5 5.0 g of quinolinic anhydride and N,N-dibenzyl-m
-Add 14.2g of Aningin to 60g of benzene and heat at 20-35°C for 20 minutes while stirring.15. , l was added.

After the addition was complete, the reaction was carried out at a temperature of 45-50'C for 5 hours.

After the reaction, 3-[2-methoxy4-dibenzylamino-benzoylcopyridinecarboxylic acid-(2) and 2-[2-methoxy-4] were treated in the same manner as in Example 3 and colored light brown. -Dibenzylamino-benzoylcopyridine-
Isomer mixture with carboxylic acid-(3) 10.6. ! i'
was obtained as a crystal.

The melting point of this crystal was 195-203°C.

This isomer mixture was prepared by the method described in Example 1.
(2-methoxy-4-dibenzylamino-benzoylcopyridine-carboxylic acid-(2)to2[2-methoxy-4
-dibenzylamino-benzoylcopyridine-carboxylic acid-(3).

4.7 g of the above 2-[2-methoxy-4-dibenzylaminobenzoylcopyridine-carboxylic acid-(3) and 2.0 g of 4-diethylamino-phenol were mixed with 100% sulfuric acid.
2g and reacted at a temperature of 90 to 95°C for 10 hours.

After the reaction, 2-[3-dibenzylamino-7diethylamino-9-oxy-xananarcopyridine-carboxylic acid-(3 ) Lactones o and B were obtained in the form of crystals.

A toluene solution of these crystals was adsorbed on acid clay and immediately developed a blue-black color.

Example 6 7.0 g of quinolinic anhydride and 11.4 g of rn-diethylamino-phenol were dissolved in 100 g of tetrachloroethane.
anhydrous aluminum chloride 19.1. ! ? added.

After the addition was completed, the reaction was carried out at a temperature of 40 to 50°C for 7 hours, then cooled to room temperature, and the reaction product was mixed with 300 rrl of ice water.
I added it inside and stirred it.

Subsequently, 100% of tetrachloroethane was added to this liquid and stirred, and the tetrachloroethane layer was collected by liquid separation.

The residue obtained by distilling off tetrachloroethane from this tetrachloroethane layer is washed with a small amount of water, followed by a small amount of petroleum ether, and dried, resulting in a pale brown color. Hydroxy-4-diethylamino-
Benzoylcopyridine-carboxylic acid-(2) and 2-[2
8.2 g of an isomer mixture with -hydroxy-4-diethylamino-benzoylcopyridine-carboxylic acid (3) were obtained in the form of crystals.

The melting point of this crystal was 211-220°C.

This isomer mixture was prepared by the method described in Example 1.
(2-hydroxy-4-diethylamino-benzoyl)pyridine-carboxylic acid-(2) and 2-(2-hydroxy-
4-diethylamino-benzoyl)pyridine-carboxylic acid (3).

The above 2-(2-hydroxy-4-diethylaminobenzoylcopyridine-carboxylic acid-(3) 3.2.9 and 4-
Di(4-methylbenzyl)aminephenol 3.2g
was added to 12 g of polyacid, 95 to 1000
The reaction was carried out at a temperature of C for 3 hours.

After the reaction, the same method as in Example 3 was carried out to obtain 2-[3-diethylamino-7-di(4-
1.0 g of the lactone of methylbenzyl)amino-9-oxyxanthylkopyridine-carboxylic acid (3) was obtained in the form of crystals.

A toluene solution of these crystals was adsorbed on acid clay and immediately developed a blue-black color.

Example 7 In Example 3, 3-(4-chloroanilino)-phenol or 3-benzylaminophenol was used instead of N-methyl-N-phenyl m-anisidine, and this was reacted with quinolinic anhydride, The corresponding pyridine-carboxylic acids, namely 3-[2-hydroxy-4(4-chloroanilino)-benzoylcopyridinecarboxylic acid-(2) and 2-[2-hydroxy-4(4-chloroanilino)-benzoylco Pyridinecarboxylic acid (
3); 3-(2-hydroxy-4-benzylamino-benzoylcopyridine-carboxylic acid-(2
) and 2-[2-hydroxy-4-benzylamino-benzoylcopyridinecarboxylic acid-(3) were prepared.

Subsequently, each of the above benzoyl-pyridine carboxylic acid isomer mixtures was isolated by the method described in Example 1.

This isolated 2-[2-hydroxy-4-(4-chloroanilino)-benzoylcopyridine-carboxylic acid-
(2) or 2-(2-hydroxy-4-benzylaminobenzoylcopyridine-carboxylic acid-(2) and 4-diethylamino-phenol were reacted and treated in the same manner as in Example 3, respectively. A pyridine-carboxylic acid lactone was obtained.

(A7 a) 2-(3-(4-chloroanilino)-7-diethylamino-9-oxyxanthyl]pyridinecarboxylic acid-(
3) Lactone.

A chloroform solution of this compound was adsorbed on acid clay and immediately developed a blue-black color.

(A7-b) 2-[3-benzylamino-7-diethylamino-9-
Lactone of oxyxanal]pyridine-carboxylic acid-(3).

A toluene solution of this compound was adsorbed on acid clay and immediately developed a blue-black color.

Example 8 In Example 3, instead of quinolinic anhydride, (a) 4
-Chloro-quinolinic anhydride, (b) 4-methylquinolinic anhydride, and (c) 6-phenyl-quinolinic anhydride are reacted with N,N-diethyl-rn-phenetidine to each the corresponding pyridine-carboxylic acid,
That is, (a): 3-(2-ethoxy-4-diethylaminohensoyl)-4-';'lolupyridine-carboxylic acid-(
2) and 2-(2-ethoxy-4-diethylamino-benzoyl)-4-chloro-pyridine-carboxylic acid-(3)
(b); 3-(2-ethoxy-4-
diethylaminobenzoyl)-4-methyl-pyridine-
Isomer mixture of carboxylic acid (2) and 2-(2-ethoxy-4-diethylamino-benzoyl)-4-methyl-pyridine-carboxylic acid (3), [c]: 3-(2-
Ethoxy-4-diethylaminobenzoyl)-6-phenyl-pyridine-carboxylic acid-(2) and 2-(2-ethoxy-4-diethylamino-benzoyl)-6-phenyl-pyridine-carboxylic acid-(3) An isomer mixture was prepared.

Subsequently, each benzoyl-pyridine-carboxylic acid isomer mixture was isolated by the method described in Example 1.

This isolated 2-(2-ethoxy-4-diethylaminobenzoyl)-4-chloro-pyridine-carboxylic acid-(3) 2-(2-ethoxy-4-diethylaminobenzoyl)-4-methyl-pyridine -Carboxylic acid- (3)
or 2-(2-ethoxy-4-diethylamino-benzoyl)-6-phenyl-pyridine-carboxylic acid-(3
) and 4-amino-phenol were reacted and treated in the same manner as in Example 3 to obtain the corresponding pyridine-phenol.
A lactone of carboxylic acid was obtained.

(As-a) 2-[3-diethylamino-7-amino-9oxy-xanthyl]-4-chloropyridinecarboxylic acid-(3)
lactone.

A toluene solution of this compound was adsorbed on acid clay and immediately developed a dark reddish-brown color.

[, 柘8-b] 2-[3-diethylamino-7-amino-9oxy-xanalyo4-methyl-pyridine-carboxylic acid = (3
) lactones.

A toluene solution of this compound was adsorbed on acid clay and immediately developed a dark reddish-brown color.

(A8 c) 2-[3-diethylamino-7-amino-9oxy-xanthyl-6-phenyl-pyridinecarboxylic acid-(3
) lactones.

A toluene solution of this compound was adsorbed on acid clay and immediately developed a dark reddish-brown color.

Example 9 1.1 of the lactone of 2[3-diethylamino-7-amino-9-oxyxanthylcopyridine-carboxylic acid-(3) with a melting point of 168 to 172°C described in Example 1 was mixed with 7.5 g of acetic anhydride. The mixture was added thereto and reacted at a temperature of 60 to 70°C for 4 hours, and then cooled to room temperature.

After cooling, the reaction product was treated in the same manner as above to obtain 2-[3-diethylamino-7-acetamido-9-oxy-xanthylkopyridinecarboxylic acid-, which is colored pale pink and is represented by the following formula. 1.0 g of the lactone (3) was obtained in the form of crystals.

The melting point of this crystal was 152-155°C.

In addition, a chloroform solution of this crystal is adsorbed on acid clay,
The color immediately developed into reddish brown.

Furthermore, when a dispersion in which these crystals were dispersed in polyvinyl acetate was heated to 120 to 1506 C, the color immediately developed into a reddish brown color.

Example 10 2-(3-diethylamino6-amino-9-oxy-xanthyrcopyridinecarboxylic acid-(3
) of lactone (A2 b) 2.09g with acetic anhydride 15g
The mixture was added thereto and reacted at a temperature of 60 to 70°C for 4 hours, and then cooled to room temperature.

After cooling, the reaction product was treated in the same manner as in Example 9 to obtain 2-[3-diethylamino-6-acetamido-9-oxy-xanthylkopyridinecarboxylic acid represented by the following formula, which is colored pale pink. −
1.9 g of the lactone (3) was obtained in the form of crystals.

A chloroform solution of these crystals was adsorbed on acid clay and immediately developed a red color.

Example 11 Lactone of 2-(3-diethylamino6-methyl-7-amino-9-oxy-xanthylkopyridine-carboxylic acid-(3)) described in Example 2 [&2- a , l 2.
Og and 1.3 g of sodium hydrogen carbonate were added to 20-7 g of water, and 1.9 g of benzyl chloride was added thereto.
The reaction was carried out at a temperature of 5°C for 8 hours and then cooled to room temperature.

After cooling, the reaction product was treated in the same manner as in Example 9 to obtain a pale yellow colored 2-[3-diethylamino-6-methyl-
2.2 g of the lactone of 7-dibenzylamino-9-oxy-xanthylkopyridine-carboxylic acid (3) was obtained in the form of crystals.

A benzene solution of these crystals was adsorbed on acid clay and immediately developed a blue-black color.

Example 12 Lactone [A2-a) of 2-[3-diethylamino6-methyl-7-amino-9-oxy-xanthylkopyridine-carboxylic acid-(3) described in Example 2] and 4-nitrobenzyl Chloride, 4-chlorobenzyl chloride or 4-methoxybenzyl chloride were reacted and treated in the same manner as in Example 11 to obtain the corresponding pyridine-carboxylic acid lactones.

[Arashi 12-a) 2-[3-diethylamino-6-methyl-7-di(4
Lactone of -nitrobenzyl)amino-9-oxyxanthylkopyridine-carboxylic acid-(3).

A toluene solution of this compound was adsorbed on acid clay and immediately developed a blue-black color.

(Al2-b) 2-[3-diethylamino-6-methyl-7-di(4
Lactone of -chlorobenzyl)amino-9-oxyxanthircopyridine-carboxylic acid-(3).

A toluene solution of this compound was adsorbed on acid clay and immediately developed a blue-black color.

(Al2-C) 2-[3-diethylamino-6-methyl-7-di(4
-methoxybenzyl)amino-9-oxy-xanthyrcopyridine-carboxylic acid-(3) lactone.

A toluene solution of this compound was adsorbed on acid clay and immediately developed a blue-black color.

Example 13 2.0.9 of the lactone (A2a) of 2-[3-diethylamino 6-methyl-7-amino-9-oxy-xanthylkopyridine-carboxylic acid-(3) described in Example 2 was dissolved in benzene 25rnI ! 1.1 g of benzoyl chloride was added to this solution and reacted at a temperature of 70 to 80° C. for 5 hours, and then cooled to room temperature.

After washing the reaction product with ice water, benzene was distilled off, and the residue was washed with a small amount of petroleum ether and dried to give a pale pink-white color of 2-[3-diethylamino-6- represented by the formula below. 2.5 g of a mixture of methyl-7-penzamide 9-oxy-xanthylkopyridine-carboxylic acid-(3) with lactone was obtained in the form of crystals.

A benzene solution of these crystals was adsorbed on acid clay and immediately developed a reddish-brown color.

Example 14 The lactone [A, 2a] 2, Og of 2-[3-diethylamino 6-methyl-7-amino-9-oxy-xanthylkopyridine-carboxylic acid-(3) described in Example 2] was dissolved in benzene 25 - and 0.7 g of triethylamine and dissolved therein, one of the eight acylating agents shown in Table 2 was added to this solution, and the mixture was reacted at a temperature of 70 to 80°C for 5 hours. I let it happen.

After the reaction, the following lactone was obtained by processing in the same manner as in Example 13.

[CAl4 a indicates the abbreviation of lactone:] Lactone of 2-[3-diethylamino-6-methyl-7cinnamamide 9-oxy-xanthyrcopyridine-carboxylic acid-(3).

[F14-b) Lactone of 2-[3-diethylamino-6-methyl-7acrylamido9-oxy-xanthylkopyridine-carboxylic acid-(3).

[A14-c] Lactone of 2-[3-diethylamino-6-methyl-7(4-methylbenzamido)-9-oxy-xanthylkopyridine-carboxylic acid-(3).

(Al4-ct) Lactone of 2-[3-diethylamino-6-methyl-7(4-chlorobenzamido)-9-oxy-xanthyrcopyridine-carboxylic acid-(3).

[A14-e] Lactone of 2-[3-diethylamino-6-methyl-7(3-nitrobenzamido)-9-oxy-xanthyrcopyridine-carboxylic acid-(3).

[:[14-f) 2-[3-diethylamino-6-methyl-7(3,4,
Lactone of (5-trimethoxybenzamide)-9oxy-xanthyrcopyridine-carboxylic acid (3).

CAl4 g) 2-[3-diethylamino-6-methyl-7(2,4-
Lactone of dimethoxybenzamide)-9-oxy-xanarcopyridine-carboxylic acid-(3).

[Arashi 14-h] Lactone of 2-[3-diethylamino-6-methyl-7(4-methoxybenzamido)-9-oxy-xanthylkopyridine-carboxylic acid-(3).

Example 15 2.5 g of the lactone (A2e) of 2-(3-dienalamino7-pendylamino-9-oxy-xanthyl)pyridine-carboxylic acid-(3) described in Example 2 was added to 10 rnl of benzene and dissolved, Add 1. 40% sodium hydroxide solution to this. Add li' and add 0.7 dimethyl sulfate.
g at a temperature of 30 to 40 °C, and after dropping 70 to 75
After reacting for 4 hours at a temperature of .degree. C., it was cooled to room temperature, and 501 rll of benzene and 15 rnl of water were added.

Next, the benzene layer is collected by liquid separation, and after washing with water, the benzene is distilled off from the benzene layer, and the residue is washed with petroleum ether and dried. 1.9 g of the lactone of 3-diethylamino-7-(N-methyl-N-benzyl)amino-9-oxy-xanthylkopyridine-carboxylic acid-(3) was obtained in the form of crystals.

A benzene solution of these crystals was adsorbed on acid clay and immediately developed a blue-black color.

Example 16 2-(3-diethylamino7-anilino-9-oxy-xanthyl)pyridine-carboxylic acid described in Example 2
(3) Lactone [P2-g32.1g to toluene 10
yd and dissolve it, add 40% sodium hydroxide solution o
, sg, and further added 1.1 g of butyl bromide,
After reacting at a temperature of 100 to 105°C for 9 hours, treatment was performed in the same manner as in Example 15 to obtain 2-[3-diethylamino-7(N
-Butyl-N-phenyl)amino-9-oxy-xanthylkopyridine-carboxylic acid-(3) lactone 2.5
9 was obtained in the form of crystals.

A toluene solution of these crystals was adsorbed on acid clay and immediately developed a blue-black color.

Claims (1)

[Claims] 1 General formula (wherein R represents a hydrogen atom or a lower alkyl group, R
1 represents a hydrogen atom, a lower alkyl group, or an optionally substituted benzyl group, R2 represents a lower alkyl group, an optionally substituted benzyl group, or a phenyl group, and R3 represents a hydrogen atom, a lower alkyl group, a halogen atom, or Represents a phenyl group. ) and a benzoyl-pyridine-carboxylic acid compound represented by the general formula (wherein R4 represents a hydrogen atom, a lower alkyl group, an optionally substituted benzyl group or a phenyl group, and R5 represents a hydrogen atom, a lower alkyl group, represents a benzyl group or acyl group substituted with , R6 represents a hydrogen atom, a lower alkyl group, or a halogen atom, R represents the same meaning as the above definition /R4, and the substitution position of the -〇R group is 6↓N\ group with the aniline compound represented by the general formula (R1, R2, R3, R,, R5
and R6 have the same meaning as defined above. ) A method for producing a novel pyridine-carboxylic acid lactone dye. 2. Producing a lactone compound of pyridinecarboxylic acid represented by the general formula (wherein R, , R2, R3, R4 and R6 have the same meanings as defined above) by the method described in claim 1. However, this compound and the general formula % (in the formula, R5 has the same meaning as the above definition, except when it is a hydrogen atom), Y is the residue of a lower alkylating agent, benzylating agent, or acylating agent. is characterized in that it is condensed with a lower alkylating agent, benzylating agent or acylating agent represented by the general formula (wherein R1, R2, R3, R4, R6 and R6 are as defined above). A method for producing a novel pyridine-carboxylic acid lactone dye represented by the same meaning (except when R5 is a hydrogen atom).