JP2006036678A - New pyrazine derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorescent dye used as an intermediate for agricultures and medicines, perfumes, polymers, etc. and a functional material, etc., for electroluminescence, light wavelength converting materials and organic functional dyes. <P>SOLUTION: A compound is represented by formula (I) [wherein R<SP>1</SP>to R<SP>4</SP>are each a hydrogen atom, a hydrocarbon group which may have a substituent group, a heterocyclic group which may have a substituent group, an acyl group, a hydrocarbon oxycarbonyl group or carbamoyl group; R<SP>1</SP>and R<SP>2</SP>and/or R<SP>3</SP>and R<SP>4</SP>may be combined to form a ring; n is 0 or 1; R<SP>5</SP>to R<SP>8</SP>are each a hydrogen atom, a hydrocarbon group which may have a substituent group, a heterocyclic group which have a substituent group, an organosilyl group, an acyl group, a hydrocarbon oxycarbonyl group, a carbamoyl group or a carbamoylcarbonyl group; R<SP>5</SP>and R<SP>6</SP>and/or R<SP>7</SP>and R<SP>8</SP>may be combined to form a ring and R<SP>5</SP>and R<SP>6</SP>and/or R<SP>7</SP>and R<SP>8</SP>together may form an imino group]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to intermediates such as agricultural medicines, fragrances, and polymers, and functional materials such as electroluminescence and wavelength conversion materials, and particularly to novel pyrazine derivatives that are useful for organic pigment dyes, banknote forgery prevention dyes, and the like.

As similar compounds of the present invention, 3,6-diamino-2,5-pyrazinedicarbonitrile derivatives are known (Patent Documents 1 to 13).
Japanese Patent Laid-Open No. 5-32640 JP-A-6-41524 Japanese Patent Laid-Open No. 6-179660 JP-A-6-38635 JP-A-7-278456 JP-A-8-143553 Japanese Patent Laid-Open No. 10-6636 Japanese Patent Laid-Open No. 11-138974 JP 2000-319265 A JP 2001-31657 A JP 2001-64530 A JP 2002-137531 A Japanese Patent Laid-Open No. 2002-2335021

  The present invention is useful for intermediates such as agricultural medicines, fragrances, and polymers, electroluminescence, light wavelength conversion materials, functional materials of organic functional dyes, and particularly used for organic pigment dyes, banknote forgery prevention dyes, etc. It aims at providing the novel compound used as the raw material of the fluorescent pigment | dye produced.

  The present inventors have found that when a compound having a cyano group at the 2-position of a pyrazine derivative is reacted with an organic halide, a novel pyrazine derivative is obtained, unlike the originally expected compound. It came to be completed.

  That is, the present invention provides (1) Formula (I)

[Wherein, R ^{1 to} R ⁴ each independently represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, an acyl group, or a hydrocarbon. Represents an oxycarbonyl group or a carbamoyl group, R ¹ and R ² , and / or R ³ and R ⁴ may combine to form a ring, n represents 0 or 1, and R ^{5 to} R ⁸ are each independently a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, an organosilyl group, an acyl group, a hydrocarbon oxycarbonyl group, Represents a carbamoyl group or a carbamoylcarbonyl group, and R ⁵ and R ⁶ , and / or R ⁷ and R ⁸ may combine to form a ring, R ⁵ and R ⁶ , and / or R ⁷ and R ⁸ together may form an imino group. ] It is related with the compound represented by this.
(2) Formula (II)

[In formula, B represents the nitrogen-containing aromatic heterocyclic ring which may have a substituent. And a compound of formula (III)

[Wherein, X represents a chlorine atom, a bromine atom, or an iodine atom, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a hydrocarbon group that may have a substituent, or a substituent. Represents a heterocyclic group, an acyl group, a hydrocarbon oxycarbonyl group, or a carbamoyl group, which may have a substituent, and R ⁹ and R ¹⁰ may combine to form a ring. And a compound represented by the formula (IV)

[Wherein, B represents the same meaning as described above, and R ¹¹ and R ¹² each independently have a hydrogen atom, a hydrocarbon group which may have a substituent, or a substituent. And may represent a heterocyclic group, an acyl group, a hydrocarbon oxycarbonyl group, or a carbamoyl group, and R ¹¹ and R ¹² may combine to form a ring. And (3) reacting the compound represented by the formula (II) with the compound represented by the formula (III) in the presence of a base (2) (4) In the formula (IV) according to (2) or (3), the method for producing the compound represented by formula (IV) according to (4), wherein B is a pyrazine ring in formula (IV) The present invention relates to a method for producing the compound represented.

  Since the compound of the present invention has strong fluorescence even in a solid state, it is expected to be applied as an organic pigment dye and a banknote forgery preventing dye, and can be said to have high industrial utility value.

The novel pyrazine derivative of the present invention is a structural formula represented by the formula (I). In formula (I), R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group that may have a substituent, a heterocyclic group that may have a substituent, an acyl group, Represents a hydrocarbon oxycarbonyl group or a carbamoyl group. Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n- Alkyl groups such as heptyl and n-octyl; vinyl, allyl, isopropenyl, 1-propenyl, 2-butenyl, 3-butenyl, 1,3-butanedienyl, 2-methyl-2- Alkenyl groups such as propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group and 3-hexenyl group; ethynyl group, 1-propynyl group, Propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 3-methyl-2-propynyl group 2-ethenylpropyl group, 2-pentyl group, 3-pentyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 1-methyl-3-butynyl group, 2-methyl-3-butynyl group, 3 -Ethynyl groups such as methyl-1-butynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group; phenyl group, 1-naphthyl group, 2-naphthyl group, etc. The alkyl group preferably has 1 to 12 carbon atoms, and the alkenyl group and alkynyl group preferably have 2 to 12 carbon atoms. be able to.

  Specific examples of the heterocyclic group include thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, quinolyl group, isoquinolyl group, benzoimidazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, pyrazinyl group. And a pyrimidinyl group, a pyridazinyl group, and the like.

  Further, the hydrocarbon group and the heterocyclic group may have a substituent on an appropriate atom, and specifically, as such a substituent, a hydroxyl group, a carboxyl group, a nitro group, a cyano group, Amino group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group; methoxy group; Alkoxy groups such as ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group and t-butoxy group; alkylamino groups such as methylamino group and ethylamino group; dimethylamino group and diethylamino group Dialkylamino groups such as methylethylamino group; aryl groups such as phenyl group, 1-naphthyl group, 2-naphthyl group; 2-pyridyl group, 3-pyridyl group Group, 4-pyridyl group, 2-quinolyl group, 3-quinolyl group, 3-isoquinolyl group and other heteroaryl groups can be exemplified, and the position of these substituents and the number of substituents are not particularly limited, When a plurality of substituents are substituted, these substituents may be the same or different.

  Specific examples of the acyl group include a formyl group, an acetyl group, a propynyl group, and a benzoyl group. Specific examples of the hydrocarbon oxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a benzyloxycarbonyl group. Specific examples of the carbamoyl group include an unsubstituted carbamoyl group, an N-methylcarbamoyl group, and an N, N-dimethylcarbamoyl group.

R ¹ and R ² , and / or R ³ and R ⁴ may be bonded to form a ring. Specifically, R ¹ and R ² are an alkyl group and bonded by an alkylene chain. when forming a cycloalkyl group, R ¹ and R ² is an acyl group, it can be exemplified a case or the like for forming a cycloalkane-dione ring attached in the alkylene chain. N represents 0 or 1.

In formula (I), R ^{5 to} R ⁸ are each independently a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or an organosilyl group. Represents an acyl group, a hydrocarbon oxycarbonyl group, a carbamoyl group, or a carbamoylcarbonyl group. Specific examples of the hydrocarbon group, the heterocyclic group, the acyl group, the hydrocarbon oxycarbonyl group, and the carbamoyl group are the same as the substituents exemplified for R ^{1 to} R ⁴ .

Specific examples of the organosilyl group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a t-butyldimethylsilyl group, and a trimethoxysilyl group. Specific examples of the carbamoylcarbonyl group include none. Examples thereof include a substituted carbamoylcarbonyl group, an N-methylcarbamoylcarbonyl group, and an N, N-dimethylcarbamoylcarbonyl group. R ⁵ and R ⁶ , and / or R ⁷ and R ⁸ may be bonded to form a ring, and as such a case, the same substituents as exemplified for R ^{1 to} R ⁴ are exemplified. be able to.

R ⁵ and R ⁶ and / or R ⁷ and R ⁸ may be combined to form an imino group. Specifically, a methylidene group, an ethylidene group, an alkoxymethylidene group, or a bis (alkylthio) methylidene group And a dialkylaminomethylidene group. Further, as R ⁵ to R ^8, it can be exemplified typically substituents used as a protecting group for an amino group.

  Specific examples of the compound represented by formula (I) of the present invention include the compounds shown in Table 1.

The method for producing the compound represented by formula (I) according to the present invention is not particularly limited. Specifically, the compound represented by formula (II) is reacted with the compound represented by formula (III). The method of making it preferable can be illustrated.

In the compound represented by the formula (II), B represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent having a cyano group on the α-position carbon of the nitrogen atom. Further, when the nitrogen-containing aromatic heterocycle is a pyrrole ring, an imidazole ring, or a pyrazole ring, the nitrogen atom may be a hydrogen atom or may be substituted with an appropriate organic group. As the substituent on the nitrogen-containing aromatic heterocyclic ring, it can be exemplified by the same as those exemplified as a substituent on a suitable atom of R ¹ to R ^4. Specific examples of the compound represented by the formula (II) include compounds represented by the following formula.

R ^{100 to} R ²¹⁶ may be the same as those exemplified as the substituents on the appropriate atoms of R ^{1 to} R ⁴ .

In the compound represented by the formula (III), X represents a chlorine atom, a bromine atom or an iodine atom, and R ⁹ and R ¹⁰ may each independently have a hydrogen atom or a substituent. Represents a hydrocarbon group, an optionally substituted heterocyclic group, an acyl group, a hydrocarbon oxycarbonyl group, or a carbamoyl group, and R ⁹ and R ¹⁰ may combine to form a ring; Specifically, the same substituents as those exemplified for R ^{1 to} R ⁴ can be exemplified.

  If the solvent used for the reaction of the compound represented by the formula (II) and the compound represented by the formula (III) is inactive with respect to the compound represented by the formula (II) and the formula (III) A solvent that can dissolve both compounds is preferable without any particular limitation. Specifically, dimethylformamide (DMF), dimethylacetamide; ethers such as dimethoxyethane and THF; aromatic solvents such as benzene, toluene, and xylene; chloroform Examples thereof include chlorinated solvents such as acetonitrile; these solvents may be used as a mixture. In some cases, the reaction can be carried out without solvent.

  When the compound represented by the formula (II) and the compound represented by the formula (III) are reacted, the reaction is preferably performed in the presence of a base. The base to be used is not particularly limited, and examples thereof include inorganic base compounds such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and organic bases such as pyridine and triethylamine. Preferable examples are alkali metal hydroxides.

The amount of the compound represented by the formula (III) to be used is not particularly limited with respect to the compound represented by the formula (II), but in order to complete the reaction, 1 mol of the cyano group in the formula (II) It is preferable to use 1 mol or more per 1 mol. In addition, when R ⁹ or R ¹⁰ is a hydrogen atom, there may be obtained a compound that is considered to have reacted with 2 mol of the compound represented by formula (III) per 1 mol of the cyano group. It is preferable to use 2 mol or more.

  Reaction temperature is not specifically limited, The range of -20-100 degreeC can be illustrated preferably. When a base is used, the addition temperature of the base is preferably low, and specifically, a range of −20 to 10 ° C. can be preferably exemplified.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Of the compounds of the present invention, Compound No. Regarding 36 and 56, the structure was determined by measuring X-ray crystallographic analysis, ¹ H-NMR, and ¹³ C-NMR. In addition, Compound No. Regarding 16, 126, and 136, the structure was determined by measuring ¹ H-NMR and ¹³ C-NMR.

Synthesis of 5- (1-cyano-1,2-di (4-phenylphenyl) ethyl) -3,6-bis (di (4-phenylphenyl) amino) pyrazine-2-carbonitrile (Compound No. 16)

1.6 g of 2,5-diamino-3,6-pyrazinedicarbonitrile and 9.9 g of p-phenylbenzyl bromide are added to 60 ml of dimethylacetamide, and the temperature is raised to 110 ° C. to dissolve once. Then, 1.6 g of powdered NaOH was added so as not to exceed 0 ° C. When the temperature did not rise, the mixture was stirred at room temperature for 1 hour. The reaction solution was added to 500 ml of saturated brine, and the resulting precipitate was filtered and further purified by column chromatography to obtain 1.0 g (yield 5.9%) of a pale yellow target product.
Melting point 243 ° C
λmax: 395 nm (CHCl ₃ )
Fmax: 515 nm (CHCl ₃ )
¹ H-NMR data (δ ppm, CHCl ₃ )
3.65 (q, 2H), 3.90 (dd, 4H), 4.85 (d, 2H), 5.30 (d, 2H), 6.80 (d, 2H), 6.90 (d, 2H), 7.10-7.65 (m, 50H)

5- (1-cyano-1,2-di- (4-bromophenyl) ethyl) -3,6-bis (di- (4-bromophenyl) amino) pyrazine-2-carbonitrile (Compound No. 36) Synthesis of

7.0 g of 2,5-diamino-3,6-pyrazinedicarbonitrile and 43.7 g of p-bromobenzyl bromide are added to 300 ml of dimethylacetamide, and the temperature is raised to 110 ° C. to dissolve once. Then, 7.3 g of powdered NaOH was added so as not to exceed 0 ° C. When the temperature did not increase, the mixture was stirred at room temperature for 1 hour. The reaction solution was added to 1200 ml of saturated brine, and the resulting precipitate was filtered and further purified by column chromatography to obtain 14.2 g (yield 27.1%) of the pale yellow target product.
Melting point 186 ° C
λmax: 392 nm (CHCl ₃ )
Fmax: 511 nm (CHCl ₃ )
¹ H-NMR data (δ ppm, CHCl ₃ )
3.28 (s, 2H), 3.72 (dd, 4H), 4.75 (d, 2H), 5.10 (d, 2H), 6.45 (d, 2H), 6.50 (d, 2H), 6.92 (d, 4H), 7.10 (d, 4H), 7.20 (d, 2H), 7.25 (d, 2H), 7.32 (d, 4H), 7.50 (d, 4H)

Synthesis of 5- (1-cyano-1,2-di- (4-chlorophenyl) ethyl) -3,6-bis (di- (4-chlorophenyl) amino) pyrazine-2-carbonitrile (Compound No. 56)

3.6 g of 2,5-diamino-3,6-pyrazinedicarbonitrile and 18.5 g of p-chlorobenzyl bromide are added to 135 ml of dimethylacetamide, and the temperature is raised to 110 ° C. to dissolve once. Then, 3.7 g of powdered NaOH was added so as not to exceed 0 ° C. When the temperature did not rise, the mixture was stirred at room temperature for 1 hour. The reaction solution was added to 800 ml of saturated brine, and the resulting precipitate was filtered and further purified by column chromatography to obtain 2.5 g (yield 12.1%) of a pale yellow target product.
Melting point 184 ° C
λmax: 392 nm (CHCl ₃ )
Fmax: 511 nm (CHCl ₃ )
¹ H-NMR data (δ ppm, CHCl ₃ )
3.30 (s, 2H), 3.75 (dd, 4H), 4.78 (d, 2H), 5.12 (d, 2H), 6.50 (d, 2H), 6.60 (d, 2H), 7.00 (d, 4H), 7.04 (d, 2H), 7.08 (d, 2H), 7.18 (m, 8H), 7.35 (d, 4H)

5- (1-Cyano-1,2-di- (4-t-butylphenyl) ethyl) -3,6-bis (di- (4-t-butylphenyl) amino) pyrazine-2-carbonitrile (compound Synthesis of No. 126)

2. 2.6 g of 2,5-diamino-3,6-pyrazinedicarbonitrile and 17.9 g of p- (t-butyl) benzyl bromide are dissolved in 100 ml of dimethylacetamide, and the temperature is lowered from −5 ° C. to 0 ° C. 2 g of powdered NaOH was added so as not to exceed 0 ° C. When the temperature did not rise, the reaction solution was added to 800 ml of saturated brine. The resulting precipitate was filtered and further purified by column chromatography to obtain 1.3 g (yield 8.3%) of a pale yellow target product.
Melting point 127 ° C
λmax: 401 nm (CHCl ₃ )
Fmax: 520 nm (CHCl ₃ )
¹ H-NMR data (δ ppm, CHCl ₃ )
1.15 (s, 9H), 1.20 (s, 9H), 1.30 (s, 18H), 1.32 (s, 18H), 3.40 (d, 2H), 3.65 (dd, 4H), 4.72 (d, 2H), 5.07 (d, 2H), 6.70 (d, 2H), 6.90-7.45 (m, 22H)

5- (1-cyano-1,2-di- (naphthalen-2-yl) ethyl) -3,6-bis (di-((naphthalen-2-yl) methyl) amino) pyrazine-2-carbonitrile ( Synthesis of Compound No. 136)

Dissolve 1.6 g of 2,5-diamino-3,6-pyrazinecarbonitrile and 9.7 g of 2-bromomethylnaphthalene in 60 ml of dimethylacetamide, lower the temperature from −5 ° C. to 0 ° C., and add 1.6 g of powdered NaOH. It added so that it might not exceed 0 degreeC, and when the temperature rise was lost, it stirred at room temperature for 1 hour. The reaction solution was added to 800 ml of saturated brine, and the resulting precipitate was filtered and further purified by column chromatography to obtain 2.2 g (yield: 8.3%) of the pale yellow target product.
Melting point 121 ° C
λmax: 395 nm (CHCl ₃ )
Fmax: 515 nm (CHCl ₃ )
¹ H-NMR data (δ ppm, CHCl ₃ )
3.75 (q, 2H), 3.95 (dd, 4H), 5.05 (d, 2H), 5.55 (d, 2H), 6.50 (d, 1H), 6.60 (d, 1H), 6.90 (d, 1H), 7.05 (d, 1H), 7.10-8.00 (m, 38H)

Claims (4)

Formula (I)
[Wherein, R ^{1 to} R ⁴ each independently represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, an acyl group, or a hydrocarbon. Represents an oxycarbonyl group or a carbamoyl group, R ¹ and R ² , and / or R ³ and R ⁴ may combine to form a ring, n represents 0 or 1, and R ^{5 to} R ⁸ are each independently a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, an organosilyl group, an acyl group, a hydrocarbon oxycarbonyl group, Represents a carbamoyl group or a carbamoylcarbonyl group, and R ⁵ and R ⁶ , and / or R ⁷ and R ⁸ may combine to form a ring, R ⁵ and R ⁶ , and / or R ⁷ and R ⁸ together may form an imino group. ] The compound represented by this. Formula (II)
[In formula, B represents the nitrogen-containing aromatic heterocyclic ring which may have a substituent. And a compound of formula (III)
[Wherein, X represents a chlorine atom, a bromine atom, or an iodine atom, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a hydrocarbon group that may have a substituent, or a substituent. Represents a heterocyclic group, an acyl group, a hydrocarbon oxycarbonyl group, or a carbamoyl group, which may have a substituent, and R ⁹ and R ¹⁰ may combine to form a ring. And a compound represented by the formula (IV)
[Wherein, B represents the same meaning as described above, and R ¹¹ and R ¹² each independently have a hydrogen atom, a hydrocarbon group which may have a substituent, or a substituent. And may represent a heterocyclic group, an acyl group, a hydrocarbon oxycarbonyl group, or a carbamoyl group, and R ¹¹ and R ¹² may combine to form a ring. ] The manufacturing method of the compound represented by this.   The method for producing a compound represented by formula (IV) according to claim 2, wherein the compound represented by formula (II) is reacted with the compound represented by formula (III) in the presence of a base. . The method for producing a compound represented by formula (IV) according to claim 2 or 3, wherein B in formula (IV) is a pyrazine ring.