JPH06172359A - Dicyanopyrrolopyrazine derivative and its production - Google Patents

Abstract

PURPOSE:To obtain the subject new compound useful as a synthetic raw material for agri chemicals, medicines, their intermediate, optical recording materials, etc., and fluorescent coloring matters, etc. CONSTITUTION:A compound of formula I [R<1> is H, (substituted) alkyl, ((substituted) cycloalkyl, (substituted) alkenyl, (substituted) alkynyl, (substituted) cycloalkenyl or (substituted) aralkyl; R<2> is OH; R<3> H; R<2> and R<3> may be bonded to form single bond; (n) is 3-4] such as compound of formula II. The compound of formula I is obtained by reacting a compound of formula III (X is halogen) with a compound of formula IV (R<4> and R<5> are lower alkyl or may be bonded to form a ring which may contain O or N).

Description

Detailed Description of the Invention

[0001]

Industrial Applicability The dicyanopyrrolopyrazine derivative obtained by the present invention is useful as a raw material for the synthesis of tetrapyrazinoporphyrazine, a fluorescent dye, etc., which is useful as an agricultural drug, an agricultural drug intermediate, or as an optical recording material, a photoelectric conversion material and the like. Is a compound useful as

[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 raw material for synthesizing tetrapyrazinoporphyrazine [Chemical Formula 8] which is useful as an optical recording material and a photoelectric conversion material.
(US 4,054,655, US 4,113,724,
(The Chemical Society of Japan 1990 (No. 2) 219 to 224, JP-A-64-34791, etc.) However, dicyanopyrrolopyrazine derivatives such as the compound of the present invention have not been synthesized until now.

[Chemical 8]

[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 intended to provide a novel dicyanopyrrolopyrazine derivative useful as a synthetic raw material such as a photoelectric conversion material and a fluorescent dye.

In the above formula, R ¹ is, for example, methyl,
1 carbon atom such as ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl, pentadecyl
~ 15 alkyl group, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
10 cycloalkyl groups such as vinyl, allyl, 2-
C2-C10 alkenyl groups such as methylallyl and 3-octenyl, for example ethynyl, 2-propynyl, 3-hexynyl and other alkynyl groups, such as cyclopropenyl and cyclohexenyl, and C3-10.
Is a cycloalkenyl group of, for example, an aralkyl group having 7 to 10 carbon atoms such as benzyl and phenylethyl. Examples of these substituents include nitro, hydroxyl group, oxo, thioxo, cyano, carbomoyl, carboxyl,
For example, C such as methoxycarbonyl and ethoxycarbonyl
_1-4 alkoxy-carbonyl, sulfo, such as fluorine,
Halogen such as chlorine, bromine and iodine, for example, lower alkoxy having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy and t-butoxy, and phenoxy, such as vinyloxy, allyloxy, 2-methylallyloxy and 2-butenyloxy. , A lower alkenyloxy having 2 to 5 carbon atoms such as 3-butenyloxy, an alkynyloxy having 2 to 5 carbon atoms such as acetylenyloxy and propargyloxy, such as o-, m- or p-chlorophenoxy, o-, halogenophenoxy such as m- or p-bromophenoxy, lower alkylthio having 1 to 4 carbon atoms such as methylthio, ethylthio, n-propylthio, isopropylthio, t-butylthio, phenylthio, C ₁ such as methylsulfinyl, ethylsulfinyl and the like. _-4 alkylsulfinyl, For example, C _1-4 alkylsulfonyl such as methylsulfonyl and ethylsulfonyl, C _2-6 acylamino such as acetylamino and propionylamino, disubstituted amino such as dimethylamino, diethylamino and N-methylanilino, such as C such as acetyl.
_2-4 Acyl, benzoyl, trialkylsilyl groups such as trimethylsilyl and triethylsilyl, and trialkyloxysilyl groups such as trimethyloxysilyl group and triethyloxysilyl group.

[0005]

The present invention has the general formula [I]

[Chemical 9] [In the formula, R ¹ is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent Is an alkynyl group which may be substituted, a cycloalkenyl group which may be substituted, or an aralkyl group which may be substituted, R ²
Is a hydroxyl group, R ³ is a hydrogen atom, or R ² and R ³
May together form a single bond, and n represents an integer of 3 to 4. ] It is a compound represented by these, and its manufacturing method.

In the present invention, the general formula [II]

[Chemical 10] [In the formula, R ¹ has the same meaning as described above, and X represents a halogen atom. ] The compound represented by the general formula [III]

[Chemical 11] [Wherein R ⁴ and R ⁵ are the same or different and each represents a lower alkyl group such as methyl or ethyl, and R ⁴ and R ⁵ are taken together to form a ring which may contain an oxygen or nitrogen atom. Also, n represents an integer of 3 to 4. In the presence of a base in a suitable solvent at a temperature of 0 ° 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, DMF, DMSO and the like are appropriately used. Further, these solvents may be mixed and used. Bases used include triethylamine, pyridine, DB
U or the like is used, but the enamine used as a raw material may also be used as a base. In addition, the general formula [IV]

[Chemical 12] [In formula, Y shows a halogen atom, such as a chlorine atom and a bromine atom, and n shows the integer of 3-4. ] And a compound represented by the general formula [V]

[Chemical 13] [In the formula, R ¹ has the same meaning as described above. ] In the presence of a base in a suitable solvent, in the case of a reaction with a compound represented by
C. to the boiling point of the solvent. As the solvent used, ethers such as THF, dioxane and dimethoxyethane, acetonitrile, esters such as ethyl acetate,
BTX solvent such as benzene and toluene, DMF, DMS
O or the like is used appropriately. Further, these solvents may be mixed and used. As the base, triethylamine, pyridine, DBU or the like is used, but the amine 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 was identified by IR, NMR, MASS, elemental analysis and the like.

[0007]

EXAMPLES Next, the present invention will be described with reference to examples. Example 1 (Compound No. 1)

[Chemical 14] 5-chloro-6- (cyclopentanone-2-yl)-
To a solution of 0.241 g of 2,3-pyrazinedicarbonitrile in benzene, 0.155 g of 40% methylamine was added dropwise at room temperature. After reacting at the same temperature for 8 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 give pale yellow crystals.
07 g were obtained. Yield 29% m. p. 162-163
℃

Example 2 (Compound No. 4)

[Chemical 15] 5-chloro-6- (cyclopentanone-2-yl)-
0.182 g of 2,3-pyrazinedicarbonitrile was dissolved in benzene, 0.146 g of n-butylamine was added at room temperature, and the reaction was further performed for 20 minutes. After the reaction was completed, the precipitated crystals were filtered off, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give pale yellow crystals.
192 g were obtained. Yield 92% m. p. 131-13
2 ° C

Example 3 (Compound No. 14)

[Chemical 16] 0.50 g of 5-chloro-6-propylamino-2,3-pyrazinedicarbonitrile was dissolved in benzene, and 0.75 g of 1-pyrrolidino-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 0.31 g of the desired product. Yield 53% m. p. 178-179 ° C

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

[Table 1]

[0011]

[Table 2]

[0012]

INDUSTRIAL APPLICABILITY The dicyanopyrrolopyrazine derivative obtained by the present invention is useful 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. Is.

Claims (3)

[Claims] 1. A compound represented by the general formula [I]: [In the formula, R ¹ is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent Represents an alkynyl group, a cycloalkenyl group which may have a substituent, an aralkyl group which may have a substituent, R ² represents a hydroxyl group, R ³ represents a hydrogen atom, or R ² and R ³ May together form a single bond, and n represents an integer of 3 to 4. ] The compound represented by these. 2. A compound represented by the general formula [II]: [In the formula, R ¹ has the same meaning as described above, and X represents a halogen atom. ] And a compound represented by the general formula [III]: [Wherein R ⁴ and R ⁵ are the same or different and each represents a lower alkyl group, and R ⁴ and R ⁵ may combine together to form a ring which may contain an oxygen or nitrogen atom, and n is It has the same meaning as described above. ] The compound represented by the general formula [I] [In the formula, R ¹ , R ² , R ³ and n 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]: [In formula, Y shows a halogen atom and n shows the same meaning as the above. ] And a compound represented by the general formula [V] [In the formula, R ¹ has the same meaning as described above. ] The compound represented by the general formula [I] [In the formula, R ¹ , R ² , R ³ and n have the same meanings as described above. ] The manufacturing method of the compound represented by these.