JP2001055391A - Benzoxazinone-based compounds and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel benzoxazinone compound for a red dye having high emission luminance and good fastness and a method for producing the same. A benzoxazinone compound represented by the following general formula (I). Embedded image (Wherein, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
_{1 to} R ₄ are not simultaneously hydrogen atoms. R represents an aryl group or a heteroaryl group which may have a substituent, and n represents an integer of 1 to 3. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a benzoxazinone compound useful as a red fluorescent dye and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, fluorescent dyes have been used for coloring various materials such as resins, dyes, inks, and the like. Applications are being developed. As the fluorescent dye, dyes having various structures and emission colors are known, but there are few compounds which emit high-luminance red light, which is required particularly in the field of electronic devices and the like, and further have excellent fastness. For example, Japanese Patent Application Laid-Open Nos. 8-298186 and 9-26828 about an organic electroluminescent device (organic EL device) using a benzoxazinone-based compound.
No. 4 discloses an example in which red light emission is obtained using a benzoxazinone-based compound represented by the following formula (D-1), but the performance as a fluorescent dye is not sufficient.

[0003]

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[0004]

In view of such circumstances, with respect to fluorescent dye compounds, there is a constant demand for the development of new dyes in order to further expand their versatility and functionality. An object of the present invention is to provide a novel compound which is useful as a red fluorescent dye having high emission luminance and excellent properties such as fastness and luminous efficiency.

[0005]

The present inventors have made intensive studies and as a result, have found that a novel benzoxazinone-based compound having an alkyl-substituted julolidine ring is a red fluorescent dye having excellent performance. The present invention has been achieved. That is, the present invention resides in a benzoxazinone-based compound represented by the following general formula (I).

[0006]

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(Wherein R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R _{1 to} R ₄ are simultaneously hydrogen atoms. R represents an aryl group or a heteroaryl group which may have a substituent, and n represents an integer of 1 to 3.) The present invention also comprises a compound of the general formula (I). The present invention also relates to a dye and a method for producing the dye.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The compound of the present invention has a structure represented by the general formula (I), and is characterized by a structure having an alkyl-substituted julolidine ring in a benzoxazinone skeleton. In the general formula (I), R ₁ , R ₂ , R ₃ , and R ₄ are the same or different and each represent a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-type group. -Represents a linear or branched alkyl group having 1 to 4 carbon atoms, such as -butyl group and t-butyl group. R _{1 to} R ₄ may be the same or different, but are not hydrogen atoms at the same time. Preferably, R _{1 to} R ₄ are alkyl groups, and particularly preferably, all of R _{1 to} R ₄ are methyl groups. R is an aryl group such as a phenyl group or a naphthyl group, or a heteroaryl group such as a furyl group, a thienyl group, or a pyridyl group, and may have a substituent. Preferably, the following general formula (II):
It is a group represented by (IIIa) or (IIIb).

[0009]

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[0010]

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(Wherein, R _{5 to} R ₁₆ each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group, a formyl group, a substituted And R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ , R
₈ and R ₉ may combine to form a ring) In the above formula, the substituents represented by R _{5 to} R ₉ are the same or different and are a hydrogen atom; for example, a chlorine atom, a bromine atom, a fluorine atom Atom, halogen atom such as iodine atom; methyl group, trifluoromethyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group,
Total carbon number 1-8, preferably 1-4, which may be substituted with halogen atoms such as t-butyl group, n-hexyl group, heptyl group, 2-ethylhexyl group and n-octyl group.
An alkoxy group having 1 to 8, preferably 1 to 4 carbon atoms corresponding to the above alkyl group such as a methoxy group or an ethoxy group; an alkoxycarbonyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms in the alkoxy moiety ;

Cyano group; formyl group; amino group, methyl
Amino group, dimethylamino group, diethylamino group, etc.
(Di) alkylamino groups. Preferably, R
_Five ~ R ₉ Are hydrogen, chlorine, bromine, fluorine
1 to 4 carbon atoms which may be substituted with an atom or a halogen atom
Alkyl group, methoxy group, cyano group, formyl group, di
It is an alkylamino group. Also, R_Five ~ R₉ Adjacent in
And the two groups may combine to form a ring. example
If R₆ Or R₇ Or R₈ When there is an amino group at the position
Has a quinoline
Or julolidine.

When R represents a naphthyl group, the substitution position on the benzoxazinone skeleton is the 1-position as in the formula (IIIa) or the 2-position as in the formula (IIIb). Examples of the substituents R _{10 to} R ₁₆ of the naphthyl group include the same substituents as R _{5 to} R _9, and a hydrogen atom, a methyl group, and a methoxy group are particularly preferable. When R represents a heteroaryl group, a thienyl group,
Furyl group, a pyridyl group are preferable, they are, R ₅ ~
The same group as R ₁₆ may be substituted. n is preferably 1 or 2. R is particularly preferably an unsubstituted or substituted phenyl group or julolidine ring with a cyano group, formyl group, or dialkylamino group. Representative examples of the compound of the present invention represented by the general formula (I) are shown in Table 1 below.
However, the compound of the present invention is not limited to these.

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

[0017]

[Table 4]

[0018]

[Table 5]

[0019]

[Table 6]

[0020]

[Table 7]

In Table 1, Me represents a methyl group and Et represents
Represents an ethyl group. The compound of the present invention represented by the general formula (I) can be produced, for example, according to the following scheme.

[0022]

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(Wherein, R _{1 to} R ₄ , R and n have the same meanings as defined in the general formula (I).) First, 8-hydroxy-9-aminodulo represented by the formula (IV) The lysine derivative is reacted with a pyruvate to obtain a benzoxazinone-based compound of the general formula (V).
The 8-hydroxy-9-aminojulolidine derivative represented by the formula (IV) is unstable as it is, and may be difficult to take out. Reducing the nitro (or nitroso) group of the 8-hydroxy-9-nitro (or nitroso) julolidine derivative to an amino group as a precursor of formula (IV),
The product can also be used as a compound of formula (IV) without separation from the reaction mixture.

The reaction is usually performed in an inert solvent.
Examples of the inert solvent used include polar solvents such as N, N-dimethylformamide, nonpolar solvents such as toluene, and lower alcohols.
Lower alcohols such as methanol and ethanol are preferred. The amount of the solvent to be used is generally 5 to 50 times by weight, preferably about 10 to 50 times by weight, relative to the above compound (IV). The reaction temperature ranges from 0 ° C to 200 ° C, preferably from room temperature to 100 ° C, and the reaction time is about 0.5 to 48 hours. After completion of the reaction, the reaction solution is cooled, and the precipitated crystals are filtered, washed with water and the like, and dried to obtain the desired product. Also,
If crystallization does not occur even after cooling, release the reaction solution into water,
The precipitated crystals are filtered, washed with water and the like, and dried to obtain the desired product. If no precipitation occurs even after release into water or the like, extraction with ethyl acetate, dichloromethane, or the like may be performed, followed by washing, drying, and concentration. The product may be purified by recrystallization or column chromatography if necessary, but it is also possible to proceed to the next step without purification.

Next, the obtained benzoxazinone compound of the formula (V) is reacted with an aldehyde of the general formula (VI) to obtain a compound of the general formula (I). The reaction is usually performed using acetic anhydride as a solvent. The amount of the solvent to be used is generally 2 to 50 times by weight, preferably 2 times, relative to compound (V).
It is preferably about 10 to 10 times by weight. Reaction temperature is from 20 ° C to 150
C., preferably around the boiling point of the solvent, and the reaction time is about 0.5 to 48 hours. After completion of the reaction, the reaction solution is cooled, and the precipitated crystals are filtered, washed with ethanol or water, and dried to obtain the desired compound of the formula (I). If crystallization does not occur even after cooling, the reaction solution is discharged into ethanol or water, and the precipitated crystals are filtered, washed with ethanol or water, and dried to obtain the desired product. If precipitation does not occur even after release into ethanol or water, extraction with ethyl acetate, dichloromethane, or the like may be performed, followed by washing, drying, and concentration. The product may be purified by recrystallization or column chromatography as necessary.

The benzoxazinone-based compound of the general formula (I) thus produced is preferably used as a water-insoluble dye. In addition to coloring various resins, paints and inks, and dyeing fibers, It is suitable for dyes such as dye lasers, organic EL (organic electroluminescence) elements, fluorescent labeling reagents, fluorescent collectors, fluorescent sensors, scintillators, and optical fiber amplifiers. Particularly, it is industrially extremely useful as a red fluorescent dye used for coloring a resin or for an organic EL device. It is also used as a synthetic intermediate of a new benzoxazinone-based fluorescent compound into which a substituent is further introduced.

[0027]

The present invention will now be described in more detail with reference to Examples.
However, the present invention is not limited to these without departing from the gist thereof.
However, the present invention is not limited to this. In the following examples,
No. of the compound Is the No. of the compound in Table 1. Corresponding to
You. Example 1 <Synthesis of Compound of Formula (V)> 1,1,7,7-tetra
Lamethyl-8-hydroxy-9-nitrosodulolidine 15
g (54.7 mmol) and tin chloride dihydrate 25.44 g (109.
4 mmol) in ethanol at 450 ° C for 5 hours
I responded. 9.52 g of ethyl pyruvate (8.2 m
mol) and 30 ml of ethanol are added dropwise.
The reaction was performed at 0 ° C. for 2 hours. Water was added to the reaction solution to precipitate
The collected crystals were collected. Ethyl acetate from the collected crude product
Concentrate the extracted liquid and use column chromatography
By purifying, the benzoxazinone compound 4.0 was obtained.
g was obtained. This product showed a vivid green fluorescence. This
Of the following NMR and MS measurements, the compound of the formula
(V) then R ₁ ~ R_Four Are all methyl group compounds
It was confirmed that. MS: m / z 312¹ H-NMR (CDCl_Three (Δ = ppm)): 1.30 (s, 6H), 1.
51 (s, 6H), 1.80 (dt, 4H), 2.45 (s, 3H), 3.22 (dt, 4H), 7.34
(s, 1H).

Example 2 <Compound No. Synthesis of 3> To 0.55 g (1.8 mmol) of the compound obtained in Example 1 and 0.36 g (2.7 mmol) of terephthalaldehyde, 2.2 ml of acetic anhydride was added and reacted at 140 ° C. for 6 hours. Water was added to the reaction solution, which was extracted with ethyl acetate. The organic layer was washed with water, dried over sodium sulfate, and concentrated. The obtained crude product was purified by column chromatography to obtain 0.01 g. Table 1 shows the results of MS measurement. 3 was confirmed. This compound showed bright orange fluorescence. MS: m / z 428 Fluorescence spectrum: λmax 603 nm (solvent: methylene chloride)

Example 3 <Compound No. Synthesis of 7> 0.13 g (0.4 mmol) of the compound obtained in Example 1 and p
-(N, N-dimethylamino) benzaldehyde 0.1
g (0.7 mmol) was added with 0.5 ml of acetic anhydride.
For 15 hours. Ethanol and water were added to the reaction solution, and extracted with ethyl acetate. The organic layer was washed with water, dried over sodium sulfate, and concentrated. The obtained crude product was purified by column chromatography, and 0.01 g
I got As a result of NMR measurement, Table 1 Compound No. 7 was confirmed. This compound showed bright red fluorescence. ¹ H-NMR (CDCl ₃ (δ = ppm)): 1.33 (s, 6H), 1.
54 (s, 6H), 1.80 (dt, 4H), 3.01 (s, 6H), 3.22 (dt, 4H), 6.71
(d, 1H), 7.25 (d, 2H), 7.40 (s, 1H), 7.54 (d, 1H), 7.85 (d, 2
H), Fluorescence spectrum: λmax 614 nm (solvent: methylene chloride).

Example 4 <Compound No. Synthesis of 2> 0.6 g (1.9 mmol) of the compound obtained in Example 1 and p-
To 0.40 g (3.1 mmol) of cyanobenzaldehyde, 2.4 ml of acetic anhydride was added and reacted at 140 ° C. for 6.5 hours. Water was added to the reaction solution, which was extracted with ethyl acetate. The organic layer was washed with water, dried over sodium sulfate, and concentrated. The obtained crude product was purified by column chromatography to obtain 0.08 g. As a result of NMR measurement, Table-
Compound No. 1 2 was confirmed. This compound showed bright orange fluorescence. ¹ H-NMR (CDCl ₃ (δ = ppm)): 1.33 (s, 6H), 1.
54 (s, 6H), 1.80 (dt, 4H), 3.30 (dt, 4H), 7.39 (s, 1H), 7.48
(d, 2H), 7.65 (m, 2H), 7.85 (d, 2H), Absorption spectrum: λmax 520 nm (solvent: methylene chloride) Fluorescence spectrum: λmax 593 nm (solvent: methylene chloride)

Example 5 <Compound No. Synthesis of 9> 0.6 g (1.9 mmol) of the compound obtained in Example 1 and 9-
2.4 ml of acetic anhydride was added to 0.62 g (3.1 mmol) of formyljulolidine and reacted at 140 ° C. for 9 hours. Water was added to the reaction solution, which was extracted with ethyl acetate. The organic layer was washed with water, dried over sodium sulfate, and concentrated. The obtained crude product was purified by column chromatography to obtain 0.01 g. Table 1 shows the results of MS measurement. It was confirmed to be 9. This compound showed bright red fluorescence. MS: m / z 495 Absorption spectrum: λmax 531 nm (solvent: methylene chloride) Fluorescence spectrum: λmax 658 nm (solvent: methylene chloride)

Example 6 <Compound No. Synthesis of 6> Compound 0.7g (2.2 mmol) obtained in Example 1 and 0.47 g (3.6 mmol) of cinnamic aldehyde were added to 2.8 acetic anhydride.
Then, the mixture was reacted at 140 ° C. for 14 hours. Water was added to the reaction solution, which was extracted with ethyl acetate. Wash the organic layer with water,
After drying with sodium sulfate, it was concentrated. The obtained crude product was purified by column chromatography,
0.1 g was obtained. Table 1 shows the results of MS measurement.
It was confirmed to be 6. This compound showed bright orange fluorescence. MS: m / z 426 Fluorescence spectrum: λmax 590 nm (solvent: methylene chloride)

Example 7 <Compound No. Coloring of Resin by 3> 0.05 g of the compound prepared in Example 2 was mixed with 100 g of polymethyl methacrylate (“Acrypet MD” manufactured by Mitsubishi Rayon Co., Ltd.), and the mixture was extruded using an extruder.
Treatment at 0 ° C. produced colored pellets. The pellets were molded by an injection molding machine at 200 ° C. for 5 minutes to produce a colored molded plate. The obtained colored plate showed a very strong fluorescent orange color, and was excellent in light resistance and migration resistance. During injection molding, the color tone of the colored plate molded in the same manner as described above except that the color plate was retained at 250 ° C. for 10 minutes showed the same color tone as that of the colored plate molded at 200 ° C. × 5 minutes. There was no change.

Example 8 <Compound No. Coloring of Resin by 7> 0.05 g of the compound prepared in Example 3 was mixed with 100 g of polymethyl methacrylate (“Acrypet MD” manufactured by Mitsubishi Rayon Co., Ltd.), and the mixture was extruded using an extruder.
Treatment at 0 ° C. produced colored pellets. The pellets were molded by an injection molding machine at 200 ° C. for 5 minutes to produce a colored molded plate. The obtained colored plate showed a very strong fluorescent red color, and was excellent in light resistance and migration resistance. During injection molding, the color tone of the colored plate molded in the same manner as described above except that the color plate was retained at 250 ° C. for 10 minutes showed the same color tone as that of the colored plate molded at 200 ° C. × 5 minutes. There was no change.

Example 9 <Compound No. 2. Coloring of Resin with 2> 0.05 g of the compound prepared in Example 4 was mixed with 100 g of polymethyl methacrylate (“Acrypet MD” manufactured by Mitsubishi Rayon Co., Ltd.), and the mixture was extruded using an extruder.
Treatment at 0 ° C. produced colored pellets. The pellets were molded by an injection molding machine at 200 ° C. for 5 minutes to produce a colored molded plate. The obtained colored plate showed a very strong fluorescent red-orange color, and was excellent in light resistance and migration resistance. During injection molding, the color tone of the colored plate molded in the same manner as described above except that the color plate was retained at 250 ° C. for 10 minutes showed the same color tone as that of the colored plate molded at 200 ° C. × 5 minutes. There was no change.

[0036]

The benzoxazinone compound of the present invention is a novel red fluorescent dye compound having high emission luminance and good fastness, and can be used for various uses of the fluorescent dye. It is extremely useful industrially as an intermediate of a fluorescent dye compound.

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Claims (5)

[Claims] 1. A benzoxazinone compound represented by the following general formula (I). Embedded image (Wherein, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
_{1 to} R ₄ are not simultaneously hydrogen atoms. R represents an aryl group or a heteroaryl group which may have a substituent, and n represents an integer of 1 to 3. ) 2. The benzoxazinone according to claim 1, wherein in the general formula (I), R is a group represented by the following general formula (II), (IIIa) or (IIIb). Compound. Embedded image Embedded image (Wherein, R _{5 to} R ₁₆ are each independently a hydrogen atom,
It represents a halogen atom, an optionally substituted alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group, a formyl group, or an optionally substituted amino group. Also, R
₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ , and R ₈ and R ₉ may combine to form a ring) 3. The benzoxazinone-based compound according to claim ₁ , wherein in the general formula (I), R _{1 to} R ₄ are methyl groups. 4. A dye comprising the benzoxazinone-based compound according to claim 1. 5. The following general formula (IV): (Wherein, R _{1 to} R ₄ have the same meanings as defined in the above general formula (I)) by reacting an 8-hydroxy-9-aminojulolidine derivative represented by the formula (I) with pyruvate esters: , The following general formula (V): (Wherein R ₁ , R ₂ , R ₃ , and R ₄ have the same meaning as defined in the general formula (I)), and a benzoxazinone-based compound represented by the following general formula: (VI) R-CHO (VI) (wherein R has the same meaning as defined in the above general formula (I)), and reacted with an aldehyde represented by the following general formula: (I) (Wherein, R _{1 to} R ₄ , R and n have the same meanings as defined above).