JPH0641135A - Imidazopteridine derivative and its production - Google Patents

Abstract

PURPOSE:To provide the novel imidazopteridine derivative useful as an intermediate raw material for agricultural chemicals, medicines, pigments, dyestuffs, etc., and as a fluorescent pigment, and capable of being simply synthesized. CONSTITUTION:A compound of formula I [R<1>, R<2> are each an alkyl, alkenyl, alkinyl, cycloalkyl, aryl, heterocyclic; R<3> is H, an alkyl, alkenyl, alkinyl, cycloalkyl; R<4> is H, an alkyl, alkenyl, alkinyl, cycloalkyl, CONHR<5> (R<5> is alkyl, alkenyl, etc.); X is NH, O (a case in which all of R<1>-R<4> are methyl and X is O, and a case in which R<1> and R<3>, R<2> and R<4>, and X are H, ethyl, and O, respectively, are excluded)], e.g. a compound of formula II. A compound of formula III (r<1> is an alkyl, alkenyl, etc.,) which is one of the compound of formula I is obtained by reacting 3,6-diamino-2,5-pyradinedicarbonitrile with a compound of formula R<1>NCO in the presence of a base. A compound of formula IV which is one of the compound of formula I is obtained by reacting a compound of formula V in the presence of a base.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel imidazopteridine derivative and a method for producing the same.

[0002]

2. Description of the Related Art Imidazopteridine derivatives have been known for a long time and there are many reports. However, most of them are related to structural isomers such as imidazo [1,2,3-ij] pteridine derivatives, imidazo [1,6-f] pteridine derivatives and imidazo [5,4-g] pteridine derivatives. However, it is only slightly known in the imidazo [4,5-g] pteridine type having the same skeleton as the compound of the present invention. They are, for example, compounds obtained by synthesis from pteridine derivatives [(Chemical formula 5),
(Chemical formula 6)] [J. Am. Chem. Soc. , 81, 2
464-71 (1959), J. Am. Chem. So
c. , 85, 1203-6 (1963)] or a compound obtained by condensation of an imidazoline derivative and a uracil derivative or a pyrimidine derivative [(Chemical formula 7), (Chemical formula 8)] [Heterocycles, 1978, 10,
45-51) and a compound disubstituted with an ethyl group [(chemical formula 9)] [Monatsh. Chem. , 1986, 11
7 (6-7), 879-82] and the like.

[0003]

[Chemical 5]

[0004]

[Chemical 6]

[0005]

[Chemical 7]

[0006]

[Chemical 8]

[0007]

[Chemical 9]

[0008]

An object of the present invention is to provide a novel imidazopteridine derivative which can be easily synthesized.

[0009]

The present inventors have found that 3,6-diamino-2,5-pyrazinedicarbonitrile [II] (Japanese Patent Application No. 2-59935) and pyrimido [4,5-g] pteridine. The derivative [IV] (Japanese Patent Application No. 4-31356) has been found first. As a result of extensive studies using these compounds [II] and [IV] as starting materials, it was found that the compound of the present invention can be easily synthesized.

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

[Chemical 10] [In the formula, R ¹ and R ² are the same or different and each may have a substituent, an alkyl group which may have a substituent, an alkynyl group which may have a substituent, a substituent A cycloalkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent, R ³ 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, a cycloalkyl group which may have a substituent, R
⁴ is 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, a cycloalkyl group which may have a substituent, Or CONHR ⁵ (R ⁵ is 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 cycloalkyl which may have a substituent) Group, an aryl group which may have a substituent or a heterocyclic group which may have a substituent), and X is N.
H or an oxygen atom (provided that R ¹ , R ² , R ³ and R ⁴ are all methyl groups and X is an oxygen atom, R ¹ and R ³
Is a hydrogen atom, R ² and R ⁴ are ethyl groups, and X is an oxygen atom. ). ] It is a compound represented by these, and its manufacturing method.

When the alkyl group, alkenyl group, alkynyl group or cycloalkyl group in R ¹ , R ² , R ³ , R ⁴ and R ⁵ has a substituent, the substituent may be, for example, a substituent. Aryl group such as phenyl group, cyano group, nitro group, alkoxy group, aryloxy group,
Examples thereof include an alkylthio group, an arylthio group and a halogen atom. When the aryl group or heterocyclic group in R ¹ , R ² or R ⁵ has a substituent, examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, a nitro group and a cyano group. , An alkylthio group, an arylthio group, an alkoxycarbonyl group, a halogen atom and the like, and those 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.

The method for producing the compound of the present invention will be described. (1)

[Chemical 11] r ¹ has the same meaning as described above. A suitable isocyanate compound is used in an amount of 3 times by mole or more with respect to the compound [II], and the reaction is carried out in an appropriate solvent at −50 ° C. to 180 ° C., preferably −20 ° C. to 150 ° C., by adding 3 times or more base. Can be obtained. As the solvent, dimethylformamide (DMF), dimethylacetamide (DMA)
C), dimethylsulfoxide (DMSO), polar solvents such as tetrahydrofuran (THF) and dimethoxyethane (DME), and the like, and they are used alone or in a mixed solvent. As the base, carbonates such as sodium carbonate and potassium carbonate, hydroxides such as sodium hydroxide and potassium hydroxide, alkoxides such as sodium methoxide and potassium t-butoxide, metal hydrogen such as sodium hydride and potassium hydride. Compounds can be used.

(2)

[Chemical 12] R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above. The compound represented by the general formula [IV] is stored in a suitable solvent at -50 ° C.
To 180 ° C., preferably −20 ° C. to 150 ° C., and can be obtained by adding and reacting a base in a catalytic amount to an equivalent amount or more. As the solvent and the base, those listed in (1) are used. After completion of the reaction, the target product can be obtained by performing a usual post-treatment. The synthesized compound was identified by NMR, IR, MASS and the like.

[0014]

EXAMPLES The present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples.

Example 1 (Compound No. 1)

[Chemical 13] Under nitrogen atmosphere, 3,6-diamino-2,5-pyrazinedicarbonitrile [II] 1.60 g (10.0 mmol)
And n-propyl isocyanate 3.8 ml (40.5 m
(mol) anhydrous DMF (15 ml) solution was ice-cooled to 60
% Oily sodium hydride 1.76 g (44.0 mm)
ol) was added. After 1.5 hours, the mixture was poured into 100 ml of ice water and acidified with dilute hydrochloric acid, and the crystals were collected by filtration and washed with ethyl acetate and then with water. The obtained reddish orange crystals were put into a mixed solvent of dichloromethane and ethyl acetate (about 3: 1 and 350 ml), well stirred, and filtered. The filtrate was concentrated under reduced pressure to give yellow crystals.
75 g (1.9 mmol) was obtained. Further, recrystallization (ethyl acetate) was performed to obtain pale yellow crystals. Yield 19%, 244 ° C (endothermic peak) ^{* *} Items with an endothermic peak or exothermic peak are D
It is the value measured by SC. (The same applies to the following examples and tables)

Example 2 (Compound No. 3)

[Chemical 14] Under a nitrogen atmosphere, 0.48 g (3.0 mmol) of 3,6-diamino-2,5-pyrazinedicarbonitrile [II] and 1.0 ml of n-butyl isocyanate (8.9 mmo).
A solution of 1) in anhydrous DMAC (15 ml) was ice-cooled to 60%.
Containing oily sodium hydride 0.60g (15.0mmo
l) was added. After 10 minutes, the temperature was raised to room temperature, and after 2 hours, 1.0 ml of n-butyl isocyanate (8.9 mmo).
l) and sodium hydride (0.60 g, 15.0 mmo)
1) was added and stirred for 10 hours. The mixture was poured into 100 ml of ice water, acidified with concentrated hydrochloric acid, and extracted with ethyl acetate. The organic layers were combined, washed with water, and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, purification was performed by silica gel column chromatography (developing solvent; benzene-ethyl acetate 1: 1) to obtain 0.58 g (1.3 mmol) of the desired product as yellow crystals.
Got Further recrystallization (dichloromethane-n-hexane)
And yellow crystals were obtained. Yield 43%, 212 ° C (endothermic peak)

Example 3 (Compound No. 6)

[Chemical 15] In a DMAC (5 ml) solution of a compound [IV] in which r ¹ , R ³ and r ⁴ are all n-butyl groups in a DMAC (5 ml) solution, 69 mg (0.
5 mmol) was added and the reaction was carried out at about 100 ° C. for 20 hours, 69 mg (0.5 mmol) of potassium carbonate was further added, and the reaction was carried out at about 150 ° C. for 6 hours. After cooling down, water 8
0 ml was added to weakly acidify with dilute hydrochloric acid, and the mixture was extracted with dichloromethane. The organic layers were combined, washed with water, and dried over anhydrous magnesium sulfate. Concentrate under reduced pressure and purify by silica gel column chromatography (developing solvent; benzene-ethyl acetate 10: 1) to obtain 0.12 g of the desired product as pale yellow crystals.
(0.27 mmol) was obtained. Yield 53%, mp 83-84 ° C

Representative examples of the compounds of the present invention, including the above examples, are shown in Table 1. In addition, Table 2 shows their fluorescent properties.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

INDUSTRIAL APPLICABILITY The compound of the present invention is useful as an intermediate raw material for agricultural medicine, pigments and dyes, or as a fluorescent dye.

Claims (3)

[Claims] 1. A compound represented by the general formula [I]: [In the formula, R ¹ and R ² are the same or different and each may have a substituent, an alkyl group which may have a substituent, an alkynyl group which may have a substituent, a substituent A cycloalkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent, R ³ 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, a cycloalkyl group which may have a substituent, R ⁴
Is 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, a cycloalkyl group which may have a substituent,
Or CONHR ⁵ (R ⁵ is 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 cycloalkyl which may have a substituent) Group, an aryl group which may have a substituent or a heterocyclic group which may have a substituent), X represents NH or an oxygen atom (provided that R ¹ , R ² , R ³ and R Except when all ⁴ are methyl groups and X is an oxygen atom, and when R ¹ and R ³ are hydrogen atoms, R ² and R ⁴ are ethyl groups and X is an oxygen atom). ] The compound represented by these. 2. 3,6-Diamino-2,5-pyrazinedicarbonitrile [II] and general formula [III] r ¹ NCO [III] (wherein r ¹ is an alkyl which may have a substituent). A group, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent or a substituent A heterocyclic group which may be present) is reacted in the presence of a base.
1] [Chemical formula 2] (In the formula, r ¹ has the same meaning as described above.) A method for producing a compound represented by the formula. 3. A compound represented by the general formula [IV]: (In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above.) The compound represented by the general formula [I-2] 4] (Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above).