JPH06179660A - Dicyanopyrazine derivative - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as an intermediate for agricultural chemicals, medicines, polymers, etc., an electroluminescent, an wavelength converting material, etc. CONSTITUTION:A compound of formula I [R<1> to R<4> are H, (substituted)- hydrocarbon, COR<5>, COOR<6>, CONR<7>R<8>, COCONR<9>R<10> (R<5> to R<10> are H, hydrocarbon, etc.)]etc., e.g. N-(5-amino-3,6-dicyanopyrazin-2-yl)cinnamamide. Furthermore, the compound of formula I is obtained by reacting, e.g. a compound of formula II with an alkylating agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel cyanopyrazine derivative. The compound of the present invention can be expected to be used as an intermediate for agricultural drugs, fragrances, polymers and the like, and can also be used as a functional material such as electroluminescence and wavelength conversion material.

[0002]

Many pyrazine derivatives having a substituted amino group and a cyano group have been reported so far, but most of them are 5,6-diamino-2,3-pyrazinedicarbonitrile [II] ), 3,5-Diamino-2,6-
Pyrazine dicarbonitrile [III] (Chemical Formula 3) or a derivative of pyrazine substituted by 1-3 amino groups or cyano groups, respectively (JP-A-1-199995).
4, U.S. Pat. No. 3,928,351), 3,6-diamino-2,5-pyrazinedicarbonitrile derivatives, such as the compounds of the present invention, emit a fluorescent color. Only the compounds listed in Table 1 are known.

[0003]

[Chemical 2]

[0004]

[Chemical 3]

[0005]

[Table 1]

[0006]

Nitrogen-containing heterocyclic compounds are a group of compounds widely used in agricultural medicine, fragrances, polymers, functional materials and the like. Among the compounds [II], [III] and other cyanopyrazine derivatives having a substituted amino group, they have been applied to agricultural drugs, raw materials for polymer synthesis, etc. (JP-A-1-199954, US Patent Specification) Book 3,
928, 351). Therefore, the compounds [II], [III
] It was expected that the 3,6-diamino-2,5-pyrazinedicarbonitrile derivative, which is a structural isomer of the above], would have the same or higher usefulness.

[0007]

The inventors of the present invention have previously found 3,6-diamino-2,5-pyrazinedicarbonitrile [IV] (Chemical Formula 4) (Japanese Patent Application No. 1-223215).
No. 2, Japanese Patent Application No. 2-59935).

[Chemical 4] As a result of extensive studies using this compound [IV] as a starting material, it was found that the compound of the present invention can be easily synthesized, and a fluorescent compound having an emission wavelength which cannot be obtained from the compounds [II] and [III] is also obtained. I found that I could be.

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

[Chemical 5][In the formula, R¹, R², R³, R^FourAre the same or different
, Hydrogen, a hydrocarbon group which may have a substituent, CO
R^Five, COOR⁶, CONR⁷R⁸, COCONR ⁹R
^Ten(R^Five, R⁶, R⁷, R⁸, R⁹, R^TenAre the same or
Are different from each other, hydrogen and a hydrocarbon group which may have a substituent.
Alternatively, it represents a heterocyclic group which may have a substituent. )
And the R¹And R², Or / and R³When
R^FourMay together form a ring. However,
R¹, R², R³, R^FourExcept for compounds in which all are hydrogen
Ku. ] It is a compound represented by these.

In the above formula, the hydrocarbon group of the "hydrocarbon group which may have a substituent" represented by R ¹ , R ² , R ³ and R ⁴ is, for example, methyl, ethyl, propyl, isopropyl, Alkyl groups having 1 to 15 carbon atoms such as butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl, pentadecyl, for example, cyclopropyl, cyclobutyl, cyclopentyl,
Cycloalkyl group having 3 to 10 carbon atoms such as cyclohexyl, alkenyl group having 2 to 10 carbon atoms such as vinyl, allyl, 2-methylallyl, and 3-octenyl, and carbon number such as ethynyl, 2-propynyl, and 3-hexynyl. Two
-10 alkynyl group, for example, cyclopropenyl, cyclohexenyl, etc., C3-C10 cycloalkenyl group, for example, benzyl, phenylethyl, etc., C7-1.
An aralkyl group of 0 is used. As the substituent of the “hydrocarbon group which may have a substituent”, for example, nitro, hydroxyl group, oxo, thioxo, cyano, carbomoyl, carboxyl, for example, C _1-4 alkoxy-, such as methoxycarbonyl, ethoxycarbonyl and the like. Carbonyl, sulfo, for example, halogen such as fluorine, chlorine, bromine, iodine,
For example, lower alkoxy having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy and t-butoxy,
Phenoxy, such as vinyloxy, allyloxy,
Lower alkenyloxy having 2 to 5 carbon atoms such as 2-methylallyloxy, 2-butenyloxy and 3-butenyloxy, for example, alkynyloxy having 2 to 5 carbon atoms such as acetylenyloxy and propargyloxy, such as o- and m-.
Or halogenophenoxy such as p-chlorophenoxy, o-, m- or p-bromophenoxy, for example, lower alkylthio having 1 to 4 carbon atoms such as methylthio, ethylthio, n-propylthio, isopropylthio, t-butylthio, phenylthio, etc. methylsulfinyl, ethylsulfinyl and the like C _1-4 alkylsulfinyl, such as methyl sulfonyl, C _1-4 alkylsulfonyl such as ethylsulfonyl, amino, for example acetylamino, C _2-6 acylamino, such as propionylamino, for example methylamino, ethyl Substituted amino such as amino, isopropylamino, n-butylamino, dimethylamino, diethylamino, cyclohexylamino and anilino, C _2-4 acyl such as acetyl, benzoyl such as trimethylsilyl, triethylsilyl and the like. Examples thereof include trialkylsilyl groups, for example, trialkyloxysilyl groups such as trimethyloxysilyl group and triethyloxysilyl group.

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰
The hydrocarbon of the “hydrocarbon group which may have a substituent” represented by is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl or decyl. , An alkyl group having 1 to 15 carbon atoms such as dodecyl and pentadecyl, for example, cyclopropyl, cyclobutyl, cyclopentyl,
Cycloalkyl group having 3 to 10 carbon atoms such as cyclohexyl, alkenyl group having 2 to 10 carbon atoms such as vinyl, allyl, 2-methylallyl, and 3-octenyl, and carbon number such as ethynyl, 2-propynyl, and 3-hexynyl. Two
Alkenyl group having 10 to 10, for example, cycloalkenyl group having 3 to 10 carbon atoms such as cyclopropenyl and cyclohexenyl, aryl group having 6 to 10 carbon atoms such as phenyl and naphthyl, and 7 carbon atoms such as benzyl and phenylethyl. Ten aralkyl groups are used. Further, as the substituent of the “hydrocarbon group which may have a substituent”, for example, nitro, hydroxyl group, oxo, thioxo, cyano, carbamoyl, carboxyl, for example, C _1-4 alkoxy-, such as methoxycarbonyl, ethoxycarbonyl and the like. Carbonyl, sulfo, halogen such as fluorine, chlorine, bromine, iodine, etc., for example, lower alkoxy having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, t-butoxy, phenoxy, for example, vinyloxy, allyloxy, 2- Methylallyloxy, 2-butenyloxy, 3
A lower alkenyloxy having 2 to 5 carbon atoms such as butenyloxy, for example, a lower alkynyloxy having 2 to 5 carbon atoms such as acetylenyloxy and propargyloxy, such as o
-, M- or p-chlorophenoxy, o-, m- or p
-Halogenophenoxy such as bromophenoxy, lower alkylthio having 1 to 4 carbon atoms such as methylthio, ethylthio, n-propylthio, isopropylthio, t-butylthio, phenylthio, C _1-4 alkylsulfinyl such as methylsulfinyl and ethylsulfinyl. , C _1-4 alkylsulfonyl such as methylsulfonyl and ethylsulfonyl, amino, C _2-6 acylamino such as acetylamino and propionylamino, such as methylamino, ethylamino, isopropylamino, n-butylamino, dimethylamino, Substituted amino such as diethylamino, cyclohexylamino, anilino, C _2-4 acyl such as acetyl, benzoyl, trialkylsilyl group such as trimethylsilyl, triethylsilyl, such as trimethyloxy. Examples thereof include trialkoxysilyl groups such as cysilyl and triethyloxysilyl. As the heterocyclic group which may have a substituent, for example, a 5- to 8-membered ring containing 1 to 5 heteroatoms such as oxygen atom, sulfur atom, nitrogen atom or a condensed ring thereof is used. Are, for example, 2- or 3-thienyl, 2- or 3-furyl, 2- or 3-pyrrolyl, 2-, 3-
Or 4-pyridyl, 2-, 4- or 5-oxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-imidazolyl, 3-, 4- Or 5-isoxazolyl, 3, -4
-Or 5-isothiazolyl, 3-or 5- (1,
2,4-oxadiazolyl), 1,3,4-oxadiazolyl, 3- or 5- (1,2,4-thiadiazolyl), 1,3,4-thiadiazolyl, 4-or 5-
(1,2,3-thiadiazolyl), 1,2,5-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1H- or 2H-tetrazolyl, N-oxide-2-, 3- Or 4-pyridyl, 2-, 4- or 5-pyrimidinyl, N-oxide-2-, 4- or 5-pyrimidinyl, 3- or 4-pyridazinyl, pyrazinyl, N-oxide-3- or 4-pyridazinyl, benzofuryl , Benzothiazolyl, benzoxazolyl, triazinyl, oxotriazinyl, tetrazolo
[1,5-b] Pyridazinyl, triazolo [4,5-
b] pyridazinyl, oxoimidazolinyl, dioxotriazinyl, pyrrolidinyl, piperidinyl, pyranyl, thiopyranyl, 1,4-oxazinyl, morpholinyl,
1,4-benzimidazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, indolizinyl, quinolidinyl, 1,8-
Naphthyridinyl, purinyl, pteridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenanthridinyl, phenazinyl, phenothiazinyl, phenoxazinyl and the like are used. Further, as the substituent of the “heterocyclic group which may have a substituent”, for example, the same or selected from those described in the substituent of the above “hydrocarbon group which may have a substituent” or the like 1 to 5 different from each other are used. What is possible among these substituents 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 compounds of the present invention can be synthesized by applying generally well-known synthetic methods. An example of a method for synthesizing them will be described below. R ¹ , R ² , R ³ , and R ⁴ are hydrogen, an alkyl group which may have a substituent, an alkenyl group which may have a substituent,
In the case of an alkynyl group which may have a substituent, it can be synthesized by reacting the compound [IV] with a suitable alkylating agent such as phosphoric acid triester or alkyl halide. It is also synthesized by reducing the Schiff base obtained by dehydration condensation with an aldehyde.

At least one of R ¹ , R ² , R ³ and R ⁴ is COR ⁵ , COOR ⁶ , CONR ⁷ R ⁸ and CO
CONR ⁹ R ¹⁰ (R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰
Has the same meaning as above. ) Is the corresponding acid chloride, acid anhydride, chloroformate,
It is synthesized by reaction with carbamic acid chloride or the like. In addition, COOR ⁶ , CONR ⁷ R ⁸ , COCONR ⁹ R ¹⁰
The compound is a compound [IV] isocyanated with phosgene, and then suitable alcohols, amines,
It can also be synthesized by reacting with anilines.

By reacting a compound having a halogen or haloacyl group (for example, α, α′-dibromo-o-xylene derivative, 1,4-diiodopentane etc.) with the compound [IV] in the same molecule. A cyclic compound containing a nitrogen atom can be synthesized. Further, these methods can be combined and synthesized, or can be synthesized by other generally known methods.

As the solvent used in these reactions,
There is no particular limitation as long as it is inert to the reaction reagent, but examples thereof include ethers such as dimethylformamide (DMF), dimethylacetamide, dimethoxyethane / THF, BTX solvents such as benzene, chlorine solvents such as chloroform, acetonitrile, alcohols. And so on. Also,
The reaction may be carried out without solvent using an excess of the reaction reagent. After the completion of the reaction, the target product can be obtained by performing a usual post-treatment. The synthesized compounds are NMR, I
It was identified by R, MASS, etc.

[0015]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 N- (5-amino-3,6-dicyanopyrazin-2-yl) cinnamamide (Compound No. 6)

[Chemical 6] 0.64 g of compound [IV] is suspended in 20 ml of pyridine,
1.1 ml of cinnamoyl chloride was added dropwise under ice cooling. Three
After 0 minutes, the reaction solution solidified, so 10 ml of pyridine was added, and the mixture was stirred for 30 minutes and then the reaction temperature was raised to room temperature.
After 5 minutes, 5 ml of methanol was added. The reaction solution was poured into water and extracted with ethyl acetate. The ethyl acetate layer was washed with water, dilute hydrochloric acid and water, and dried over anhydrous magnesium sulfate. Ethyl acetate was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: benzene / ethyl acetate = 5/1) to obtain 0.22 g of the desired product. Yield 20% DSC 257 ° C (endothermic peak), 261 ° C (exothermic peak)

Example 2 N- (5-amino-3,6-dicyanopyrazin-2-yl) -3-methylbenzamide (Compound No. 14)

[Chemical 7] 0.96 g of the compound [IV] is suspended in 20 ml of pyridine,
2.44 g of m-toluoyl chloride was added dropwise under ice cooling.
After reacting for 3 hours, 5 ml of methanol was added. The reaction solution was poured into water and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine and dried over anhydrous magnesium sulfate. Ethyl acetate was evaporated under reduced pressure, and the residue was purified by silica gel chromatography (eluent: benzene / ethyl acetate = 5/1) to obtain 0.74 g of the desired product. Yield 45% DSC 238 ° C (endothermic), 244 ° C (exothermic)

Example 3 2-Amino-3,6-dicyano-5-bis (ethoxycarbonyl) aminopyrazine (Compound No. 52)

[Chemical 8] 0.8 g of compound [IV] was suspended in 15 ml of pyridine, and 1.19 g of ethyl chloroformate was added dropwise under ice cooling. 5-10
After reacting for 3 hours at ℃, the reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. After washing the ethyl acetate layer with water, the ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 0.8 g of the desired product. Yield 5
2.6% m.p. p. 108-109 ° C

Example 4 3,6-bis (di- (4-t-
Butylbenzyl) amino) -2,5-pyrazinedicarbonitrile (Compound No. 78)

[Chemical 9] 0.48 g of the dried compound [IV] and 3.8 ml of 4-t-butylbenzyl bromide dimethylacetamide (15
0.1 ml of powdery 96% sodium hydroxide under ice cooling.
63 g was added in small portions. After reacting for 15 minutes, ice water 1
The mixture was poured into 00 ml and extracted with dichloromethane. The dichloromethane layer was washed with water and dried over anhydrous magnesium sulfate.
Dichloromethane was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (eluent: benzene / hexane = 3/2) to obtain 0.82 g of the desired product. Yield 37% m. p. 211-213 ° C

Including the above examples, Table 2 shows typical examples of the compounds of the present invention together with their fluorescent properties.

[0020]

[Table 2]

[0021]

[Table 3]

[0022]

[Table 4]

[0023]

[Table 5]

[0024]

[Table 6]

[0025]

[Table 7]

[0026]

[Table 8]

[0027]

[Table 9]

[0028]

[Table 10]

[0029]

[Table 11]

[0030]

[Table 12]

[0031]

[Table 13]

[0032]

[Table 14]

[0033]

[Table 15]

[0034]

[Table 16]

[0035]

[Table 17]

[0036]

[Table 18]

[0037]

INDUSTRIAL APPLICABILITY The compound of the present invention can be expected to be used as an intermediate for agricultural medicines, fragrances, polymers and the like, and can also be used as a functional material such as electroluminescence and wavelength conversion material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C07D 405/14 241 8829-4C 409/12 241 8829-4C 409/14 241 8829-4C 413/12 241 8829-4C 417/12 241 9051-4C 417/14 241 9051-4C 471/04 103 E 8829-4C 114 A 8829-4C C07F 7/10 S 8018-4H

Claims (1)

[Claims] 1. A compound represented by the general formula [I]: [In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and are hydrogen, a hydrocarbon group which may have a substituent, CO
R ⁵ , COOR ⁶ , CONR ⁷ R ⁸ , COCONR ⁹ R
¹⁰ (R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are the same or different and may have hydrogen, a hydrocarbon group which may have a substituent, or a substituent. A heterocyclic group), R ¹ and R ² , or / and R ³ and R
⁴ may together form a ring. However, R ¹ ,
Excludes compounds in which R ² , R ³ and R ⁴ are all hydrogen. ]
The compound represented by.