JPH0665213A - Dicyanopyrazine derivative and its production - Google Patents

Abstract

PURPOSE:To provide a new dicyanopyrazine derivative useful as a synthetic raw material for tetrapyrazinoporphyrazine which is useful as an agrichemicals, pharmaceuticals, intermediate for agrichemicals and pharmaceuticals, optical recording material, photoelectric conversion material, etc., and as a fluorescent pigment, etc. CONSTITUTION:The compound of formula I [R<1> and R<2> are H, alkyl or aryl; R<3> and R<4> are alkyl, alkenyl or alkynyl; A is halogen or XR<5> [X is O, S or NR<6> (R<6> is H, alkyl, alkenyl, alkynyl or aryl); R<5> is H, alkyl, alkenyl, alkynyl or aryl], R<1> and R<2>, R<1> and R<3> or R<4>, R<2> and R<3> or R<4>, or R<3> and R<4> may together form an (O or S-containing) ring], e.g. 5-chloro-6-[2-(N,N- diethylamino)-1-vinyl]-pyrazine-2,3-dicarbonitrile. The compound of formula I wherein A is Y (Y is halogen) can be produced by reacting a compound of formula II with a compound of formula III.

Description

Detailed Description of the Invention

[0001]

Industrial Applicability The dicyanopyrazine derivative obtained by the present invention is used as an agricultural drug, an agricultural drug intermediate, or as a synthetic raw material of tetrapyrazinoporphyrazine useful as an optical recording material, a photoelectric conversion material, and a fluorescent dye. It is a useful compound.

[0002]

2. Description of the Related Art Many compounds of 2,3-dicyanopyrazine derivatives have been synthesized so far. For example, a compound in which the 5-position has been substituted with an alkylamino group or a phenylthio group has been found to have bactericidal activity and the like.
A compound whose position is substituted with alkyl, aryl or the like is used as a synthetic raw material of tetrapyrazinoporphyrazine useful as an optical recording material or a photoelectric conversion material (see Chemical formula 14). (US 4,054,655, US 805,
150, Journal of the Chemical Society of Japan 1990 (No. 2) 219
~ 224, JP-A-64-34791, etc.)

[Chemical 14] However, a compound substituted with a substituent having an aminovinyl structure, such as the compound of the present invention, has not been synthesized until now.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is as an agricultural drug or an intermediate thereof, or an optical recording material,
It is to provide a novel dicyanopyrazine derivative useful as a synthetic raw material such as a photoelectric conversion material and a fluorescent dye.

[0004]

Means for Solving the Problems As a result of intensive studies using 5,6-dihalogenopyrazinedicarbonitrile and its derivatives as raw materials, it was found that the compound of the present invention can be easily obtained by reaction with an enamine or a tertiary amine. The present invention has been completed.

That is, the present invention has the general formula [I]

[Chemical 15] [Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, and R ³ and R ⁴ are the same or different. Differently, they represent an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, A is a halogen atom or XR ⁵ {X is an oxygen atom. ,
Sulfur atom, NR ⁶ (R ⁶ is a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent,
The alkynyl group which may have a substituent and the aryl group which may have a substituent are shown. And R ⁵ represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or an alkyl group which may have a substituent. It represents a good aryl group. }, And R ¹
And R ² , R ¹ and R ³ or R ⁴ , R ² and R ³ or R ⁴ , or R ³ and R ⁴ together form an oxygen atom, a sulfur atom, NR ⁷ (R ⁷ has a substituent An optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group) may be included to form a ring. ] It is a compound represented by these, and its manufacturing method.

Examples of the compound represented by the general formula [I] include the compounds shown in the following [Chemical formula 16] to [Chemical formula 36], which may further have a substituent. Examples of the group include an alkyl group which may have a substituent,
Examples thereof include an aryl group such as a phenyl group which may have a substituent, a cyano group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a nitro group and a halogen atom. What is possible among these groups may further have a substituent. The number of substituents and the bonding position thereof are arbitrary, and when a plurality of substituents are bonded, they may be the same or different from each other.

[0007]

[Chemical 16]

[0008]

[Chemical 17]

[0009]

[Chemical 18]

[0010]

[Chemical 19]

[0011]

[Chemical 20]

[0012]

[Chemical 21]

[0013]

[Chemical formula 22]

[0014]

[Chemical formula 23]

[0015]

[Chemical formula 24]

[0016]

[Chemical 25]

[0017]

[Chemical formula 26]

[0018]

[Chemical 27]

[0019]

[Chemical 28]

[0020]

[Chemical 29]

[0021]

[Chemical 30]

[0022]

[Chemical 31]

[0023]

[Chemical 32]

[0024]

[Chemical 33]

[0025]

[Chemical 34]

[0026]

[Chemical 35]

[0027]

[Chemical 36]

General formula [I-1]

[Chemical 37] [In the formula, R ¹ , R ² , R ³ , R ⁴ and Y have the same meanings as described above. ] In the production of the compound represented by the general formula [I
I]

[Chemical 38] [In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above. ] The compound and 5,6-dihalogeno-2,3 represented by
-In the case of reaction with pyrazine dicarbonitrile, it is carried out in the presence of a base in a suitable solvent at a temperature between 0 ° C and the boiling point of the solvent. As the solvent used, THF, dioxane,
Ethers such as dimethoxyethane, esters such as acetonitrile and ethyl acetate, BT such as benzene and toluene
X-based solvent, DMF, DMSO, etc. are appropriately used. Further, these solvents may be mixed and used. As the base, triethylamine, DBU, pyridine, etc. are used, but the enamine used as a raw material may also be used as the base. In addition, the general formula [IV]

[Chemical Formula 39] [In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above. ] The compound and 5,6-dihalogeno-2,3 represented by
-In the case of the reaction with pyrazine dicarbonitrile, it is carried out in a suitable solvent in the presence or absence of an oxidizing agent, at a temperature of 0 ° C to the boiling point of the solvent. The solvent used is T
Ethers such as HF, dioxane and dimethoxyethane,
Esters such as acetonitrile and ethyl acetate, BTX solvents such as benzene and toluene, DMF, DMSO and the like are appropriately used. Further, these solvents may be mixed and used. Benzoyl peroxide, N
-Bromosuccinimide or the like is used.

General formula [I-2]

[Chemical 40] [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X have the same meanings as described above. ] In the production of the compound represented by the general formula [I-1]

[Chemical 41] [In the formula, R ¹ , R ² , R ³ , R ⁴ and Y have the same meanings as described above. ] And a compound represented by the general formula [V]

[Chemical 42] [In the formula, X and R ⁵ have the same meanings as described above. ] In the case of the reaction with the compound represented by the formula, it is carried out in the presence of a base in a suitable solvent at a temperature of -20 ° C to the boiling point of the solvent. As the solvent used, ethers such as THF, dioxane and dimethoxyethane, esters such as acetonitrile and ethyl acetate, BTX solvents such as benzene and toluene, DM
F, DMSO or the like is used as appropriate. Further, these solvents may be mixed and used. When X is an oxygen atom and R ⁵ is lower alkyl, that is, lower alcohol, this alcohol may also be used as a solvent. As the base, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride, and organic bases such as triethylamine, pyridine and DBU are used, and when X is an oxygen atom, the corresponding bases are used. Alkoxides may be used.

General formula [I-2]

[Chemical 43] [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X have the same meanings as described above. ] In the production of the compound represented by the general formula [II]

[Chemical 44] [In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above. ] The compound and general formula [VI]

[Chemical formula 45] [In the formula, X, Y and R ⁵ have the same meanings as described above. ] In the case of the reaction with the compound represented by the formula, it is carried out in the presence of a base in a suitable solvent at a temperature of -20 ° C to the boiling point of the solvent. Examples of the solvent used include ethers such as THF, dioxane and dimethoxyethane, esters such as acetonitrile and ethyl acetate, BTX solvents such as benzene and toluene, D
MF, DMSO, etc. are appropriately used. Further, these solvents may be mixed and used. As the base, triethylamine, DBU, pyridine, etc. are used, but the enamine used as a raw material may also be used as the base. After completion of the reaction, the target product can be obtained by performing usual treatment. The structure of the obtained compound is IR, NMR, MAS
It was identified by S, elemental analysis and the like.

[0031]

EXAMPLES Next, the present invention will be described with reference to examples. Example 1 5-Chloro-6- [2- (N, N-diethylamino) -1-vinyl] -pyrazine-2,3-dicarbonitrile (Compound No. 2)

[Chemical formula 46] 1.5 g of 5,6-dichloropyrazine dicarbonitrile was dissolved in DMF, and 1.5 g of triethylamine was added dropwise at room temperature. After reacting for 20 hours at the same temperature, the precipitated crystals were filtered off and the residue was purified by silica gel column chromatography to obtain 0.44 g of the desired product. Yield 22% m. p. 146-148 ° C

Example 2 5-Chloro-6- [2-pyrrolidino-1-cyclohexenyl] -pyrazine-2,3-dicarbonitrile (Compound No. 5)

[Chemical 47] 1.0 g of 5,6-dichloropyrazinedicarbonitrile was dissolved in benzene, and 1.51 g of 1-pyrrolidino-1-cyclohexene was added dropwise at room temperature. After further reacting for 5 minutes at the same temperature, the precipitated crystals were filtered off, and the filtrate was concentrated under reduced pressure.
The residue was recrystallized from ethyl acetate to obtain 1.48 g of the desired product. Yield 94% m. p. 186-187 ° C

Example 3 5-Chloro-6- (2-morpholino-1-cyclohexenyl) -pyrazine-2,3-dicarbonitrile (Compound No. 6)

[Chemical 48] 1.0 g of 5,6-dichloropyrazinedicarbonitrile was dissolved in benzene, and 1.67 g of 1-morpholino-1-cyclohexene was added dropwise at room temperature. After further reacting at the same temperature for 5 hours, the precipitated crystals were filtered off, and the filtrate was concentrated under reduced pressure.
The residue was purified by silica gel column chromatography to obtain 1.51 g of the desired product. Yield 91% m. p. 127-129 ° C

Example 4 5-Chloro-6- (1-methyl-1,2,3,4-tetrahydropyridin-5-yl)
-Pyrazine-2,3-dicarbonitrile (compound number
7)

[Chemical 49] 0.4 g of 5,6-dichloropyrazinedicarbonitrile was dissolved in benzene, 0.6 g of N-methylpiperidine was added at room temperature, and then 0.5 g of benzoyl peroxide was added little by little under cooling. After the temperature was returned to room temperature and the reaction was continued for 2 hours, the reaction mixture was washed with water and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography and recrystallized from ethanol to obtain 0.15 g of the desired product. Yield 29% m. p. 158 ~ 160 ℃

Examples of compounds according to the present invention including the above-mentioned examples are shown in Table 1.

[Table 1]

[0036]

INDUSTRIAL APPLICABILITY The dicyanopyrazine derivative obtained by the present invention is used as an agricultural drug, an agricultural drug intermediate, or as an optical recording medium, an electrophotographic material, a photosensitive material for a laser printer,
It is useful as a redox catalyst or a synthetic raw material of tetrapyrazinoporphyrazine which is useful as a flower, cut flower, a freshness-maintaining agent for foods, and a fluorescent dye.

Claims (5)

[Claims] 1. A compound represented by the general formula [I]: [Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, and R ³ and R ⁴ are the same or different. Differently, they represent an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, A is a halogen atom or XR ⁵ {X is an oxygen atom. ,
Sulfur atom, NR ⁶ (R ⁶ is a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent,
The alkynyl group which may have a substituent and the aryl group which may have a substituent are shown. And R ⁵ represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or an alkyl group which may have a substituent. It represents a good aryl group. }, And R ¹
And R ² , R ¹ and R ³ or R ⁴ , R ² and R ³ or R ⁴ , or R ³ and R ⁴ together form an oxygen atom, a sulfur atom, NR ⁷ (R ⁷ has a substituent An optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group) may be included to form a ring. ] The compound represented by these. 2. A compound represented by the general formula [II]: [Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, and R ³ and R ⁴ are the same or different. Differently, they represent an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and R ¹ and R ² , R ¹ and R ³ or R ⁴ , R ² and R ³
Alternatively, R ⁴ , or R ³ and R ⁴ together form an oxygen atom, a sulfur atom, NR ⁷ (R ⁷ is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a substituent A ring may be formed with or without (indicating an alkynyl group which may have a group). ] And a compound represented by the general formula [III]: [In formula, Y shows a halogen atom. ] The compound represented by the general formula [I-1] [In the formula, R ¹ , R ² , R ³ , R ⁴ and Y have the same meanings as described above. ] The manufacturing method of the compound represented by these. 3. A compound represented by the general formula [IV]: [Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, and R ³ and R ⁴ are the same or different. Differently, they represent an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and R ¹ and R ² , R ¹ and R ³ or R ⁴ , R ² and R ³
Alternatively, R ⁴ , or R ³ and R ⁴ together form an oxygen atom, a sulfur atom, NR ⁷ (R ⁷ is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a substituent A ring may be formed with or without (indicating an alkynyl group which may have a group). ] The compound represented by the general formula [III] [In formula, Y shows a halogen atom. ] The compound represented by the general formula [I-1] [In the formula, R ¹ , R ² , R ³ , R ⁴ and Y have the same meanings as described above. ] The manufacturing method of the compound represented by these. 4. A compound represented by the general formula [V]: [In the formula, X is an oxygen atom, a sulfur atom, NR ⁶ (R ⁶ is a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent which may have a substituent). Represents a good alkynyl group or an aryl group which may have a substituent), and R ⁵ represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a substituent The alkynyl group which may have a group and the aryl group which may have a substituent are shown. ] The compound represented by the general formula [I-1] [In the formula, R ¹ , R ² , R ³ , R ⁴ and Y have the same meanings as described above. ] The compound represented by the general formula [I-2]: [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X have the same meanings as described above. ] The manufacturing method of the compound represented by these. 5. A compound represented by the general formula [II]: [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom,
An alkyl group which may have a substituent and an aryl group which may have a substituent, R ³ and R ⁴ are the same or different, and an alkyl group which may have a substituent and a substituent which may have a substituent. An alkenyl group which may be substituted or an alkynyl group which may have a substituent, R ¹ and R ² , R ¹ and R ³ or R ⁴ , R ² and R ³
Alternatively, R ⁴ , or R ³ and R ⁴ together form an oxygen atom, a sulfur atom, NR ⁷ (R ⁷ is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a substituent A ring may be formed with or without (indicating an alkynyl group which may have a group). ] And a compound represented by the general formula [VI]: [In the formula, R ⁵ , X and Y have the same meanings as described above. ] The compound represented by the general formula [I-2]: [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X have the same meanings as described above. ] The manufacturing method of the compound represented by these.