JPS6039096B2 - Bispirolopyrazine compounds, methods for their preparation and methods for using them as pigments - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a bispirolopyrazine compound, and more specifically to a bispirolopyrazine compound represented by the general formula (1) (wherein R is a hydrogen atom, a methyl group, a furyl group, or a phenyl group, and X is a hydrazine residue or The present invention relates to novel and valuable bis(5-oxo-2,3-disubstituted 1aH-pyrrolo[3,4b]pyrazine-7-imidyl) compounds represented by carbocyclic aromatic diamine residues.

R in the general formula (1) is a hydrogen atom, a methyl group, a furyl group, or a phenyl group, and × is N of ink N・NH2
A hydrazine residue or general formula ratio N that means a bond between -N
It is a residue R' of an aromatic diamine represented by -R'-N (where R' represents a carbocyclic aromatic group).

Examples of the aromatic diamine include the following compounds. ○-Phenylenediamine, m-phenylenediamine, P-phenylenediamine, 4,4'-diami/diphenyltriphenyl, aluene, 4,4'-diaminodiphenyl, 4,4'-diaminostilbene , 1,4-diaminonaphthalene, 1,8-diaminonaphthalene, 3
・6-diaminonaphthalene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 2,6-diaminopyridine, 206-diaminocarbazole, 2.
6-diaminobenzothiazole, 3,6-diaminoacridine, and alkyl groups such as methyl, ethyl, and t-butyl on the carbon ring of these compounds, substituted hydroxyl groups such as methoxy, ethoxy, and phenoxy, halogen, carpoxyl group, Aromatic diamines having substituents such as nitro and cyano groups.

Furthermore, the present invention relates to a method for producing a bispirrolopyrazine compound represented by general formula (1).

That is, this product is a 7-amino-
2,3-di-substituted-5-oxopyrrolo[3,4b]pyrazine (in the formula, R has the meaning of the above) and general formula (m)
CIH・日2N−×−NH2・HC1 (m
) (wherein, X has the meaning described above) by condensing carbocyclic aromatic diamine dihydrochloride or hydrazine dihydrochloride in an organic solvent.

The 7-amino-2,3-disubstituted-5-oxopyrrolo[3,4b]pyrazine represented by the general formula (D) used in the present invention is diaminomaleonitrile (DAMM), which has recently become possible to produce industrially. 5 and 6 substitutions derived from -
2-cyanopyrazine-3-carboxyamide is dissolved in a lower aliphatic alcohol in the presence of a lower aliphatic alkoxide at room temperature or under heating, and neutralized with an acid containing almost no water such as acetic acid. It can be produced with high yield.

In addition, the compound represented by general formula (b) can also be represented as the following tautomer.

The other raw material used in the present invention, the compound represented by the general formula (m), is hydrazine dihydrochloride or carbocyclic aromatic diamine dihydrochloride. This carbocyclic aromatic diamine hydrochloride can be obtained by converting the aromatic diamine into a hydrochloride using a conventional method. In order to deepen the color tone of the bispirrolopyrazine compound represented by the general formula (1), 5-oxo-2,3-disubstituted pair-pyrrolo[3,4b
] A diamino compound that produces a conjugated double bond system in association with the pyrazine ring may be selected. The method for producing a bispirrolopyrazine compound represented by the general formula (1) according to the present invention is a method for producing a bispirrolopyrazine compound represented by the general formula (b) using a 7-amino-2,3-disubstituted-5-oxopyrrolo[3,4b]pyrazine The diamine dihydrochloride represented by formula (m) is prepared by reacting hydrazine dihydrochloride in an organic solvent according to the following reaction formula.

This condensation reaction proceeds at a relatively low temperature, but the reaction temperature is
It is desirable to set it as 5000 or more, especially 100-200 qo.

In addition, this condensation reaction is carried out in an organic solvent, but for example, when carried out in a halogenated organic solvent, the diamine is dissolved in the solvent with a free amine, hydrogen chloride gas is introduced to form diamine dihydrochloride, and then the reaction is carried out. You can. The organic solvent used in the condensation reaction is an inert solvent that does not participate in the condensation reaction, such as toluene, xylene, benzene, carbon tetrachloride, benzene chloride, dioxane, tetralin, dichloroethane, trichloroethane, nitrobenzene, acetic acid, Ethanol, n-butanol, ethylene glycol,
Examples include aromatic hydrocarbons, halogenated hydrocarbons, nitrated hydrocarbons, aliphatic alcohols, lower aliphatics, ethers, and esters, such as ethylene glycol dimethyl ester.

Bispi produced in this way and represented by general formula (1).

Most of the lopyrazine compounds are bright deep yellow to light yellow solids, and most of them have melting points of 300°C or higher.They also have pigment suitability such as sunlight resistance, solvent resistance, acid resistance, and alkali resistance. It is also superior to isoindolinone pigments, which are widely used as pigments. For this purpose, printing inks and paints can be produced by kneading the compounds according to the invention with natural or synthetic vehicles and, if necessary, adding pigment auxiliaries. In addition, when converting this bispirolopyradiso compound into a pigment, the compound is ground with an inorganic salt grinding aid such as sodium chloride or calcium chloride in a ball mill, etc., and then washed with water to remove the inorganic salt. Pigments with improved tinting power etc. can be obtained by treatment such as heating and rinsing in an organic solvent such as benzene. It is also possible to color these base materials by dispersing them in rubber, synthetic resins, etc. The present invention will be further explained below with reference to Examples.

Example 1100 A Class 4 flask was charged with 2.0 g of 7-amino-5-oxopyrrolo[3,4b]pyrazine, 1.3 g of p-phenylenediamine dihydrochloride, and 60 g of ○-dichlorobenzene, and the mixture was heated to 140 ~ It was held at 150 points for 5 hours.

Thereafter, the reaction solution was cooled to 100 to 110 q0, and the light yellow crystals precipitated at the same temperature were collected, thoroughly washed with 50% each of acetone, methanol, ethanol, and water, and then dried to a deep light yellow color. 3.01 minutes of a substance exhibiting the following were obtained. The physical properties of this product were as follows. Melting point: 30 p0 or higher Elemental analysis value: (%) C, 8 days, C days as 8N802
N analysis value 58.28 2.66 29.97 calculated value 58. Spot 2.70 30.27 Infrared absorption spectrum: (KB, enemy-1) 319 stop 3 female 0, 1745
1675 1498, 1375, 1 I 5, 129 and above 12
3113fu840 etc. N Satoshi (mass spectrometry): (m/e
) 370 From the above results, the product has the following structure: 4,4'-bis(5-oxo).

It was (3.small) pyrazine-7-imidoyl)benzene. This compound had excellent suitability as a pigment.

Example 2 Into a 100 [Type 4 flask], 2.0 liters of 7-amino-5-oxopyrrolo[3,4b]pyrazine, 2.8 liters of hydrazine dihydrochloride, and 60 liters of ethyl alcohol were charged.
It was kept under reflux for 2 hours at 80°C.

The crystals were sewn at the same temperature, thoroughly washed with 50 parts each of ethanol, acetone, methanol, and water, and then dried to obtain 1.5 parts of yellow crystals. The physical properties of this product were as follows. Melting point: 300oo or higher Elemental analysis value: (%) C, 2 days C as 6N802 N analysis value 48.70 2.41 37.92 Calculated value 48.98 2.04 38.09 Infrared absorption spectrum: (KBr, skin -1) 3250, 1750, 1
SS (mass spectrometry) to N such as 665, 161514751350, 1135: (m/e) 294 From the above results, the product has the following structure. ] pyrazine-7-imidoyl)hydrazine.

This compound had suitability as a pigment.
Example 3 2.0 ml of 7-amino-2,3-dimethyl-5-oxopyrrolo[3,4b]pyrazine was added to a four-faced flask of LOOO.
1.5 hours of p-phenylenediamine dihydrochloride and 60 hours of -dichlorobenzene were charged and maintained at 130 to 1320 degrees for 1 hour.

After cooling to 100°C, the obtained green-yellow crystals were washed thoroughly with 50 parts each of acetone, ethanol, methanol, and water, and dried.

Yield 1.5 evenings. The physical properties of this product were as follows. Melting point: 300qo or higher Elemental analysis value: (%) C22 days, 8
C day N analysis value 61.41 4.0 as N802
1 25.91 calculated value 61.97 4.23 2
6.29 Infrared absorption spectrum: (KBr, suppression-1) 3
42u 3160, 299 stop 1740, 1670, 1
500, 1 paper 0, 1330, 124fu 1140, 99
5N Satoshi (mass spectrometry): (m/e) 426 From the above results, the product has the following structure: 4,4-pis(5-oxo-2,3-dimethyl-mother H-pyrrolo[3,
4b] pyrazine-7-imidoyl)benzene.

This compound was suitable as a raw material.
In the reactions of Examples 4 to 23, the raw materials and reaction conditions were changed to obtain the products shown in the following table.

Test Example 1 JIS for some of the compounds obtained in Examples 1 to 23
．． A pigment suitability test was conducted according to the method of K5101 (pigment test method).

The test pieces used for the tinting power and sunlight hardness tests were prepared as follows. That is, a fullshade printing ink was prepared by kneading 1.00 g of the compound and 1.50 g of No. 4 linseed oil 500 times in a Hubermaller. In addition, a light color (
A tintingshade ink was prepared. Apply 1.5cc of both inks to test printing paper (Kent paper) for 52cm.
The color was applied to an area of 5c skin and used. The results of this pigment suitability test are shown in the table below.

Pigment suitability test table

Claims (1)

[Claims] 1 General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is a hydrogen atom, a methyl group, a furyl group, or a phenyl group, and X is a hydrazine residue or a carbon A bis(5-oxo-2,3-disubstituted-6H-pyrrolo[3,4b]pyrazine-7-imidoyl) compound represented by a cyclic aromatic diamine residue. 2 General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents a hydrogen atom, a methyl group, a furyl group, or a phenyl group), 7-amino-2.3
-Disubstituted-5-oxopyrrolo[3,4b]pyrazine and general formula (III) ClH.H_2N-X-NH_2.HCl
(III) (wherein, X represents a hydrazine residue or a carbocyclic aromatic diamine residue) is reacted with diamine dihydrochloride or hydrazine dihydrochloride in an organic solvent. General formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is a hydrogen atom, methyl group, furyl group, or phenyl group, and X is a hydrazine residue or a carbocyclic aromatic diamine residue A method for producing a bis(5-oxo-2,3-disubstituted-6H-pyrrolo[3,4b]pyrazin-7-imidoyl) compound represented by 3. The production method according to claim 2, wherein the organic solvent is a halogenated hydrocarbon, a nitrated hydrocarbon, an aliphatic alcohol, or a lower fatty acid. 4 General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R is a hydrogen atom, methyl group, furyl group, or phenyl group, and X is a hydrazine residue or a carbocyclic aromatic diamine residue. bis(5-oxo-
2,3-disubstituted-6H-pyrrolo[3,4b]pyrazine-
A method in which a 7-imidoyl) compound is used as a pigment to produce a dispersion paint by mixing it with a vehicle, or for coloring by blending it into rubber or synthetic resin.