JP3047551B2 - Cyanopyrazine derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to novel cyanopyrazine derivatives. The compound of the present invention can be expected to be used as an intermediate for agricultural chemicals, fragrances, polymers, and the like, and is expected to be used as a functional material such as electroluminescence and a wavelength conversion material.

[0002]

2. Description of the Related Art Although a large number of pyrazine derivatives having a substituted amino group and a cyano group have been reported so far, most of them are 5,6-diamino-2,3-pyrazinedicarbonitrile [II] (formula 2). ), 3,5-diamino-2,6-
Pyrazine dicarbonitrile [III] or
It is a derivative of pyrazine substituted with 1-3 amino groups or cyano groups, respectively (JP-A-1-199954, U.S. Pat. No. 3,928,351), and 3,6-diamino as in the compound of the present invention. -2,5-Pyrazinedicarbonitrile derivatives have not been known so far.

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[0003]

The nitrogen-containing heterocyclic compounds are a group of compounds widely used in agricultural medicines, fragrances, polymers, functional materials and the like. Among the above-mentioned compounds [II], [III] and other cyanopyrazine derivatives having a substituted amino group, application to agricultural chemicals, raw materials for polymer synthesis, etc. has been made (Japanese Patent Application Laid-Open No. 1-199954, U.S. Pat. Book 3,
No. 928,351). Therefore, the compounds [II], [III
3,6-diamino-2,5-pyrazinedicarbonitrile derivative, which is a structural isomer, was expected to have the same or higher utility.

[0004]

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

Embedded image As a result of intensive 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 that cannot be obtained from the compounds [II] and [III] was also obtained. Was found to be able to.

That is, the present invention provides a compound represented by the general formula [I]:

Embedded image [Wherein, R ¹ , R ² , R ³ , and R ⁴ are the same or different and each have a hydrogen atom, an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, or a substituent. Alkynyl group, trialkylsilyl group, COR ⁵ , COOR
⁶ , CONR ⁷ R ⁸ (R ⁵ , R ⁶ , R ⁷ , and R ⁸ are the same or different and are hydrogen, an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, R ¹ and R 2 represent an alkynyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent. ² or /
And R ³ and R ⁴ may together form a ring,
Further, R ¹ and R ² or / and R ³ and R ⁴ together form = C (R ⁹ ) OR ¹⁰ , = CHNR ¹¹ R ¹² , =
SR ¹³ R ¹⁴ , = C (SR ¹⁵ ) ₂ (R ⁹ , R ¹⁰ , R ¹¹ , R
¹² , R ¹³ , R ¹⁴ , and R ¹⁵ may be the same or different and represent an alkyl group or an aryl group). However, compounds in which R ¹ , R ² , R ³ , and R ⁴ are all hydrogen are excluded. ] It is a compound represented by these.

The compounds of the present invention can be synthesized by applying generally well-known synthetic methods. Examples of these synthesis methods are described below: R ¹ , R ² , R ³ , and R ⁴ are hydrogen, an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, a substituent In the case of an alkynyl group which may have
V] with a suitable alkylating agent, for example, a phosphoric acid triester, an alkyl halide or the like. It is also synthesized by reducing a Schiff base obtained by dehydration condensation with an aldehyde.

At least one of R ¹ , R ² , R ³ , R ⁴ is COR ⁵ , COOR ⁶ , CONR ⁷ R ⁸ (R ⁵ ,
R ⁶ , R ⁷ and R ⁸ have the same meaning as described above. ) Is synthesized by reaction with the corresponding acid chloride, acid anhydride, chloroformate, carbamic acid chloride or the like. Further, the compounds of COOR ⁶ and CONR ⁷ R ⁸ can also be synthesized by isocyanating the compound [IV] with phosgene and then reacting it with an appropriate alcohol, amine or aniline.

A compound in which at least one pair of R ¹ and R ₂ and R ³ and R ⁴ is ＣC (R ⁹ ) OR ¹⁰ , wherein R ⁹ and R ¹⁰ have the same meanings as described above, is a compound [ IV] and an orthoester (eg, ethyl orthoformate, methyl orthoacetate, etc.).

A compound in which at least one pair of R ¹ and R ₂ and R ³ and R ⁴ is ＣＨCHNR ¹¹ R ¹² (R ¹¹ and R ¹² have the same meaning as described above) is a compound [IV] and OHCNR ¹¹
It is synthesized by a condensation reaction of R ¹² or a reaction of an imidate type compound obtained by the above reaction with an amine or aniline.

A compound in which at least one pair of R ¹ and R ₂ and R ³ and R ⁴ is ＳＲSR ¹³ R ¹⁴ (R ¹³ and R ¹⁴ have the same meanings as described above) corresponds to the compound [IV]. With sulfides and sulfoxides.

A compound in which at least one pair of R ¹ and R ₂ and R ³ and R ⁴ is ＣC (SR ¹⁵ ) ₂ (R ¹⁵ has the same meaning as described above) is a compound [IV] and carbon dioxide And an alkyl halide.

Reacting a compound having a halogen or a haloacyl group in the same molecule (for example, α, α'-dibromo-o-xylene, 1,4-diiodobutane, phthaloyl dichloride, etc.) with the compound [IV] Thus, a cyclic compound containing a nitrogen atom can be synthesized.

When at least one of R ¹ , R ² , R ³ and R ⁴ is a trialkylsilyl group, it is synthesized by reaction with a trialkylsilyl chloride. Furthermore,
These methods can be combined for synthesis, or can be synthesized by other generally known methods.

The solvents used in these reactions include:
There is no particular limitation so long as it is inert to the reaction reagent. Examples thereof include dimethylformamide (DMF), dimethylacetamide, ethers such as dimethoxethane / THF, BTX solvents such as benzene, chlorine solvents such as chloroform, acetonitrile, and alcohols. Is mentioned. Further, the reaction may be carried out without a solvent by using an excess of the reaction reagent.
After completion of the reaction, the desired product can be obtained by performing ordinary post-treatment. The synthesized compounds are NMR, IR,
It was identified by MASS or the like.

[0015]

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 (Compound No. 4) (R ¹ , R ² ) = (R ³ , R ⁴ ) =

Embedded image 0.40 g of compound [IV], 16 ml of DMF and α, α'-
A mixture of 1.45 g of dibromo-o-xylene was added with ice cooling,
0.45 g of oily sodium hydride (containing 60%) was added. After reacting at the same temperature for 40 minutes and further at room temperature for 1.5 hours, the mixture was poured into iced water, and the formed crystals were collected by filtration, washed with water and ethyl acetate, and dried to obtain 0.65 g of a target product of red crystals. Yield 71% mp 318 ° (endothermic) ^* * Measured by DSC (the same applies to the following Examples and Table 1)

Example 2 (Compound No. 7) R ¹ ＣＯCOCH ₃ R ² ＲR ³ ＲR ⁴ ＨH (Compound No. 8) R ¹ ＲR ² ＣＯCOCH ₃ R ³ ＲR ⁴ ＨH (Compound No. 9) ) R ¹ ＲR ³ ＣＯCOCH ₃ R ² ＲR ⁴ ＨH: 1.4 g of compound [IV] was heated to reflux in 30 ml of acetic anhydride for 8 hours. After completion of the reaction, excess acetic anhydride and generated acetic acid were distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using benzene-ethyl acetate 2: 1 as an elution melt. 1.35 g of compound No. 7 in the order of elution
(Yield 63%), compound No. 8 (0.41 g, yield 23%), compound No. 9 (0.13 g, yield 6)
%). mp Compound No. 7 269 ° (endothermic) 274 ° (exothermic) Compound No. 8 190 ° (endothermic) 231 ° (exothermic) Compound No. 9 267-268 ° C. (decomposition)

Example 3 (Compound No. 18) (R ¹ , R ² ) = (R ³ , R ⁴ ) =

Embedded image 0.64 g of the compound [IV] was added to 15 ml of pyridine, and 1.79 g of phthalic chloride was gradually added under ice-cooling. The reaction temperature was gradually raised and the reaction was carried out at room temperature for 4 hours. The reaction mixture was poured into ice water, and the precipitate was collected by filtration and washed with water. The obtained crude crystals were recrystallized from DMF to obtain 1.0 g of the desired product. Yield 60% mp 363 ° (endothermic)

Example 4 (Compound No. 21) (R ¹ , R ² ) = (R ³ , R ⁴ ) == CHOC ₂ H ₅ (Compound No. 22) (R ¹ , R ² ) == CHOC ₂ H ₅ , R ³ = CHO, R ⁴ = H: A mixture of 0.4 g of the compound [IV], 15 ml of ethyl orthoformate and 5 drops of trifluoroacetic acid was heated under reflux for 5 minutes. After completion of the reaction, excess ethyl orthoformate and generated ethanol were distilled off under reduced pressure, and the residue was recrystallized with a mixed solvent of benzene and hexane to obtain 0.45 g of compound No. 21 as yellow crystals. Yield 66% mp 145-147 ° C. Meanwhile, the recrystallized mother liquor was concentrated and then purified by silica gel column chromatography to obtain Compound No. 22 (0.4%).
1 g was obtained. Yield 16% mp 170-179 ° C

Example 5 (Compound No. 23) (R ¹ , R ² ) =＝ CHOC ₂ H ₅ , R ³ ＣＯCOCH ₃ , R ⁴ ＨH: 2.05 g of compound No. 8 was added to ethyl orthoformate.
A mixture of 6.7 ml and 10 drops of trifluoroacetic acid was heated to reflux for 31 hours. After completion of the reaction, excess ethyl orthoformate and generated ethanol and the like are distilled off under reduced pressure, and the residue is purified by silica gel chromatography to obtain the desired compound 1.
7 g were obtained. (Yield 65%) mp 173-176 ° C

Example 6 (Compound No. 26) (R ¹ , R ² ) = (R ³ , R ⁴ ): = CHN (CH ₃ ) ₂ (Compound No. 27) (R ¹ , R ² ) = CHN (CH ₃ ) ₂ , R ³ = R ⁴ = H: 0.5 g of compound [IV] is added to 5 ml of dioxane and 2 ml of benzene.
Was added, and then 0.92 g of DMF was added.
Under ice-cooling, oxalyl chloride (1.0 g) was gradually added dropwise. After reacting at 10 to 20 ° C. for 1 hour, the precipitated crystals were collected by filtration. Next, the obtained crystals are suspended in ethyl acetate,
Neutralized with 0.6 g of triethylamine. The precipitated crystals were collected by filtration and recrystallized from a mixed solvent of acetonitrile-ethyl acetate to obtain 0.28 g of orange crystals (Compound No. 26). Yield 33% mp 304 ° (endothermic) On the other hand, the mother liquor filtered after neutralization was concentrated and purified by column chromatography to give orange crystals (Compound No. 27).
21 g were obtained. Yield 31% mp247 ° (endothermic)

Example 7 (Compound No. 29) (R ¹ , R ² ) = (R ³ , R ⁴ ): = S (CH ₃ ) ₂ : 0.32 g of the compound [IV] was mixed with 3 ml of dimethyl sulfoxide and 1 ml of methylene chloride. And cooled to 0 ° C.
Then, 0.76 g of oxalyl chloride was added dropwise. 10
After reacting at ２０20 ° C. for 1 hour, 1.8 g of triethylamine was added, and stirring was further continued for 30 minutes. The reaction mixture was poured into ice water, and the precipitated crystals were collected by filtration, washed with water, methanol, acetone, and DMF, and then dried to obtain the desired product 0.4.
0 g was obtained. Yield 71% mp 234 ° (exothermic)

Example 8 (Compound No. 31) (R ¹ , R ² ) = (R ³ , R ⁴ ) == C (SCH ₃ ) ₂ : 0.8 g of the compound [IV] is added to 40 ml of DMF,
After cooling to −20 ° C., 1.76 g of carbon disulfide and 3.55 g of methyl iodide were added. Next, oily sodium hydride (6
(0% content) was added and reacted at the same temperature for 3 hours. After the completion of the reaction, the reaction solution was poured into ice water and the precipitate was collected by filtration. This was thoroughly washed with water and acetone to obtain 1.45 g of the desired product. (Yield 79%) mp 284 ° (endothermic)

Table 1 shows typical examples of the compound [I], including the compounds of the above Examples, and Table 2 shows the fluorescence characteristics. In Table 2, the solvent used for measuring UV and emission wavelength was dimethoxyethane (compound numbers 1, 3, 8, 15, 16,
21, 24, 25, 32), CH ₃ CN (Compound No. 1)
7, 19, 27), methylene chloride (Compound No. 14),
Acetone (Compound No. 30), and all quantum yields were measured using methylene chloride as a solvent. In Table-3,
The absorption wavelength and fluorescence emission wavelength of the compound of Compound No. 1 and its structural isomer are shown.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4]

[0028]

[Table 5]

[0029]

[Table 6]

[0030]

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

Continuation of the front page (72) Inventor Tomio Yagihara 345 Yanagimachi, Takada, Odawara-shi, Kanagawa Japan Soda Corporation Odawara Research Laboratories (56) References JP-A-5-4974 (JP, A) JP-A-1-199954 (JP) , A) JP-A-50-19761 (JP, A) WO 93/9664 (WO, A1) WO 91/3469 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 241/26 C07D 241/28 C07D 403/04 C07F 7/10 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A compound of the general formula [I] [Wherein, R ¹ , R ² , R ³ , and R ⁴ are the same or different and each have a hydrogen atom, an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, or a substituent. Alkynyl group, trialkylsilyl group, COR ⁵ , COOR
⁶ , CONR ⁷ R ⁸ (R ⁵ , R ⁶ , R ⁷ , and R ⁸ are the same or different and are hydrogen, an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an optionally substituted alkynyl group, an optionally substituted aryl group or a substituent shown also good heterocyclic group.), a group represented by also, R ¹ and R R ² and / or R ³ and R ⁴ may together form a ring, and R ¹ and R ² or / and R ³ and R ⁴ together form ＝ C (R ⁹ ) OR ¹⁰ , = CHNR ¹¹ R ¹² , = SR
¹³ R ¹⁴ , = C (SR ¹⁵ ) ₂ (R ⁹ , R ¹⁰ , R ¹¹ , R ¹² ,
R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different and each represents an alkyl group or an aryl group). However, compounds in which R ¹ , R ² , R ³ , and R ⁴ are all hydrogen are excluded. ] The compound represented by these.