JP2000319265A - New cyanopyrazine derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound emitting intense fluorescence even in a solid state, and useful as an intermediate for agrochemicals/medicaments, perfumes, polymers, etc., a functional material such as organic functional dye, in particular a dye for preventing bill forgery, as a fluorescent dye or the like used as an organic pigment dye or the like. SOLUTION: This new compound is a compound of formula I [A1 to A4 are each a (substituted)aryl or the like; R1 to R8 are each H, a (substituted)aryl or the like; wherein excepting the case that all of A1 to A4 are each 2-F-phenyl, 4-Br-henyl, 4-cyano-phenyl, p-tolyl or nonsubstituted naphthyl, and all of R1 to R8 are each H], e.g. a compound of formula II. The compound of formula I is obtained by reaction between a compound of the formula X-CH2-A' (X is a halogen, methylsulfo or the like; A' has the same meaning as those of A1 to A4) (e.g. benzyl bromide) and 3,6-diamino-2,5-pyrazinedicarbonitrile in the presence of a deacidifier (e.g. an inorganic basic compound such as sodium hydroxide, organic base such as pyridine or triethylamine).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The compound of the present invention relates to intermediates such as agrochemicals, fragrances and polymers, and functional materials such as light wavelength conversion materials, electroluminescence and organic functional dyes.

[0002]

2. Description of the Related Art As a compound according to the present invention, a pyrazine derivative having a substituted amino group and a cyano group is known, and a 3,6-dicyano-2,5-pyrazinedicarbonitrile derivative (III) is disclosed in -32640, JP-A-7-278456 and Dyes. Pigm. (19
98), 39 (4), 341-357. However, the compound according to the present invention is not known.

[0003]

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[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide functional materials such as agrochemicals, fragrances, intermediates such as polymers, light wavelength conversion materials, electroluminescence, and organic functional dyes. An object of the present invention is to provide a fluorescent dye used as a forgery prevention dye, an organic pigment dye, or the like.

[0005]

Means for Solving the Problems The present inventors have proposed 3,6-
Diamino-2,5-pyrazinedicarbonitrile

[0006]

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As a starting material, the compounds of the present invention have been found, and a compound having strong fluorescence which cannot be obtained from the conventional 3,6-dicyano 2,5-pyrazinedicarbonitrile derivative has been found. That is, the present invention provides a compound represented by the general formula (I):

[0008]

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(Wherein A ¹ , A ² , A ³ and A ⁴ represent an optionally substituted aryl group or an optionally substituted heteroaryl group, and R ¹ , R ² , R ³ , R ^{4, R 5, R 6,} R 7,
R ⁸ independently represents a hydrogen atom, an optionally substituted aryl group, or an optionally substituted heteroaryl group. However, when A ¹ , A ² , A ³ , and A ⁴ are all 2-F-phenyl, 4-Br-phenyl, 4-cyano-phenyl, p-tolyl, or unsubstituted naphthyl, Except when all of R ^{1 to} R ⁸ are hydrogen atoms. ). The general formula (II)

Embedded image(Wherein X is a halogen atom such as chlorine, bromine, iodine,
Methylsulfo group, trifluoromethylsulfo group, p-to
A 'represents a ruene sulfo group;¹, A^Two, A^Three, A ^FourSame as
Indicates the same meaning. ) And 3,6-diamido
No-2,5-pyrazinedicarbonitrile and deoxidizing agent present
General formula (I) characterized by reacting under

Embedded image (In the formula, A ¹ , A ² , A ³ , and A ^{4 each} represent an optionally substituted aryl group or an optionally substituted heteroaryl group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, an optionally substituted aryl group, or an optionally substituted heteroaryl group, provided that A ¹ , A ² , A ³ , A ⁴ are all 2-F-phenyl, 4-Br-phenyl, 4-cyano-phenyl, p-tolyl or unsubstituted naphthyl, all R ^{1 to} R ⁸ are hydrogen atoms Is a method for producing a compound represented by the formula:

Hereinafter, the present invention will be described in detail. In the general formula (I), A ¹ , A ² , A ³ , and A ⁴ each represent an optionally substituted aryl group or an optionally substituted heteroaryl group. Phenyl group, 1-naphthyl group, 2-naphthyl group, 2
-Pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-
Examples thereof include a quinolyl group, a 3-quinolyl group, and a 3-isoquinolyl group. The aryl group or the heteroaryl group may have a substituent, and examples of the substituent include methyl, ethyl, propyl, isopropyl,
C _1-6 alkyl groups such as butyl and t-butyl; and halogen atoms such as fluorine, chlorine, bromine and iodine.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ represent a hydrogen atom, a benzyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 2-picolyl group, Represents an aryl group such as a picolyl group, a 4-picolyl group, a 2-quinolylmethyl group, a 3-quinolylmethyl group, a 3-isoquinolylmethyl group, or a heteroaryl group. The aryl group and the heteroaryl group may have a substituent, and the substituent may be methyl, ethyl, propyl, isopropyl, butyl, t-
Examples thereof include a C _1-6 alkyl group such as butyl and a halogen atom such as fluorine, chlorine, bromine and iodine.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention can be synthesized by applying a known synthesis method. The methods for their synthesis are described below. General formula (II)

[0012]

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(Wherein X is chlorine, bromine, iodine, etc.)
Logen atom, methyl sulfo group, trifluoromethyl sulf
A ′ represents a p-toluenesulfo group, and A ′ represents A¹, A^Two,
A^Three, A ^FourHas the same meaning as ) And the compound represented by
3,6-diamino-2,5-pyrazinedicarbonitrile

[0014]

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Can be synthesized by using an appropriate deoxidizing agent.

As the deoxidizing agent, inorganic base compounds such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, as well as organic bases such as pyridine and triethylamine are used.

The solvent used in these is not particularly limited as long as it is inert to the reaction reagent. Examples thereof include dimethylformamide (DMF), dimethylacetamide, ethers such as dimethoxyethane / THF, benzene, toluene, xylene and the like. Aromatic solvents, chlorinated solvents such as chloroform, and acetonitrile. These may be used as a mixture, or the reaction may be carried out without a solvent using an excess of the reaction reagent.

After completion of the reaction, the desired product can be obtained by performing a usual treatment. Table 1 shows compounds that can be synthesized by the above production method. In the table, Ph is a phenyl group, t
Bu represents a t-butyl group, and Me represents a methyl group.

[0019]

[Table 101]

[0020]

[Table 102]

[0021]

[Table 103]

[0022]

[Table 104]

[0023]

[Table 105]

[0024]

[Table 106]

[0025]

[Table 107]

The synthesized compound is identified by NMR, IR and MS.

[0027]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 3-dibenzylamino-6-N (α, α-dibenzyl)
Production of benzyl-benzylamino-2,5-pyrazinedicarbonitrile (Compound No. I-1)

Embedded image 0.8 g (5 mmol) of 3,6-diamino-2,5-pyrazinedicarbonitrile was added to 20 m of dimethylacetamide.
After cooling the solution to -5 ° C, 5.64 g (0.033 mol) of benzyl bromide was divided into three portions.
To 0 ° C. One hour after aging, 80 ml of ice water
Opened. To this, 50 ml of toluene was added for extraction. The toluene layer was washed with water until the liquid became transparent, concentrated and allowed to stand to form crystals. The crystals were filtered and dried to obtain 1.7 g of yellow crystals (yield: 48%). Melting point 68-70.5 ° C ¹ H-NMR data (δ ppm, CDCl ₃ ): 3.46 (dd, 2H), 3.71
(dd, 4H), 4.85 (d, 2H), 5.15 (d, 2H), 6.67 (d, 2H), 6.81 (d, 2
H), 7.05-7.36 (m, 26H)

Example 2 Preparation of 3,6-bis [{α, α-di (4′-t-butylbenzyl)} amino] -2,5-pyrazinedicarbonitrile (Compound No. I-87)

Embedded image 0.8 g (5 mmol) of 3,6-diamino-2,5-pyrazinedicarbonitrile was added to 20 m of dimethylacetamide.
l. After cooling this solution to -5 ° C, 11.3 g (0.05 mol) of pt-butylbenzylbromide was added. Then 2.4 g of 96% sodium hydroxide powder
(0.05 mol) was divided into three portions and added in the range of -5 to 0 ° C. After aging at 10 ° C or less for 2 hours, the mixture was poured into 80 ml of ice water. To this, 50 ml of toluene was added for extraction. Thereafter, the same treatment as in Example 1 was carried out to obtain 4.2 g of yellow crystals. Yield 42%. 120-122 ° C.

Reference Example 1 3,6-bis {di (2-fluorobenzyl) amino}-
Production of 2,5-dipyrazinecarbonitrile (Compound No. I-17)

Embedded image 0.8 g (5 mmol) of 3,6-diamino-2,5-pyrazinedicarbonitrile was added to 20 m of dimethylacetamide.
After cooling the solution to -5 ° C, 4.15 g (0.02 mol) of 2-fluorobenzyl bromide was added. Next, 0.83 g of powdered 96% sodium hydroxide (0.
02 mol) was added in two portions in the range of -5 to 0 ° C. One hour after aging, it was poured into 80 l of ice water. To this, toluene 50
ml was added for extraction. The same treatment as in Example 1 was performed to obtain 1.74 g of a red-orange compound. 138-140 ° C.

Example 3 3-[{(α, α-dibenzyl)-(2′-fluorobenzyl)}-(2′-fluorobenzyl)] amino-6
Preparation of -di (2'-fluorobenzyl) amino-2,5-pyrazinedicarbonitrile (Compound No. I-37)

Embedded image The crystals (3 mmol) obtained in Reference Example 1 were further added to DMF2
0 g of benzyl bromide 1.1 g (6 mmol
l) Added. Next, powder 96% sodium hydroxide 0.25
g (6.6 mmol) was added in two portions and added in the range of -5 ° C to 0 ° C. After aging for 1 hour at 10 ° C or lower, the mixture was poured into 80 ml of ice water. To this, 50 ml of toluene was added for extraction. This reaction solution was treated in the same manner as in Example 1 to obtain 1.47 g of yellow crystals.
Obtained. Yield 31%.

[0031]

Since the compound of the present invention has strong fluorescence even in a solid state, it is expected to be applied as a fluorescent pigment and a dye for preventing forgery of banknotes.

Claims (2)

[Claims] 1. A compound of the general formula (I) (In the formula, A ¹ , A ² , A ³ , and A ^{4 each} represent an optionally substituted aryl group or an optionally substituted heteroaryl group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, an optionally substituted aryl group, or an optionally substituted heteroaryl group, provided that A ¹ , A ² , A ³ , A ⁴ are all 2-F-phenyl groups, 4
A -Br-phenyl group, a 4-cyano-phenyl group, a p-tolyl group or an unsubstituted naphthyl group, except that all of R ^{1 to} R ⁸ are hydrogen atoms. ). 2. A compound of the general formula (II)(Wherein X is a halogen atom such as chlorine, bromine, iodine,
Methylsulfo group, trifluoromethylsulfo group, p-to
A 'represents a ruene sulfo group;¹, A^Two, A^Three, A ^FourSame as
Indicates the same meaning. ) And 3,6-diamido
No-2,5-pyrazinedicarbonitrile and deoxidizing agent present
2. The compound according to claim 1, which is reacted under the following conditions.
Manufacturing method.