JPS6247460B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to pyrazoloazaxanthenoisoquinolinones. The following general formula of the present invention [] (In the formula, R ¹ represents a hydrogen atom, an alkyl group, a trifluoromethyl group, an alkoxycarbonyl group, an alkoxycarbonylalkyl group, an aralkyl group, or a phenyl group, and R ² represents an alkoxycarbonyl group that may have a substituent. R ³ represents a lower alkyl group, a cyclohexyloxycarbonyl group, a tetrahydrofurfuryloxycarbonyl group, an aryloxycarbonyl group, a benzyloxycarbonyl group, an acyl group, a cyano group, or a carbamoyl group which may have a substituent. The pyrazoloazaxanthenoisoquinolinones represented by the following formula are themselves novel compounds with extremely strong fluorescence, and are valuable as dyes or dyes. To explain the present invention in detail, the compound of the present invention has the general formula [] (In the formula, R ¹ and R ² have the same meanings as in the above general formula [], and X represents a halogen atom.) 2-pyrrolidone,
In an organic solvent inert to the reaction such as N/N-dimethylformamide or quinoline, optionally in the presence of a deoxidizing agent such as sodium carbonate, potassium carbonate or triethylamine, the following general formula [] (In the formula, R ³ has the same meaning as in the general formula []) and pyridones of 100 to
It is produced by reacting at a temperature of 200°C, preferably 140-160°C. The reaction product can be easily isolated as crystals by diluting it with methanol, water, etc., as the case may be. Examples of the substituent represented by R ¹ in the general formulas [] and [] include a hydrogen atom;
Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group; trifluoromethyl group; alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group; methoxycarbonyl Examples include alkoxycarbonylalkyl groups such as methyl group, ethoxycarbonylmethyl group, propoxycarbonylmethyl group, butoxycarbonylmethyl group; phenyl group; aralkyl groups such as benzyl group and phenethyl group; R ² is methoxycarbonyl group, ethoxy Alkoxycarbonyl groups such as carbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group;
methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, propoxyethoxycarbonyl group, butoxyethoxycarbonyl group, methoxypropoxycarbonyl group, methoxyethoxyethoxycarbonyl group, ethoxyethoxyethoxycarbonyl group, propoxyethoxyethoxycarbonyl group, butoxyethoxyethoxycarbonyl group,
Alkoxy groups such as dimethylaminoethoxycarbonyl group and diethylaminoethoxycarbonyl group,
an alkoxycarbonyl group substituted with an alkoxyalkoxy group, an alkylamino group, etc.;
Cyclohexyloxycarbonyl group; Tetrahydrofurfuryloxycarbonyl group; Benzyloxycarbonyl group; Aryloxycarbonyl group such as tolyloxycarbonyl group and phenoxycarbonyl group; Acyl group such as acetyl group, benzoyl group, and thienoyl group; Cyano group ;Carbamoyl group; phenylcarbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, propylcarbamoyl group,
Examples include substituted carbamoyl groups such as a butylcarbamoyl group, a dimethylcarbamoyl group, a diethylcarbamoyl group, and a morpholinocarbonyl group. Examples of the substituent represented by R ³ in the general formulas [] and [] include a methyl group, an ethyl group, a linear or branched propyl group, and a butyl group. Further, examples of the substituent represented by X in the general formula [] include a chlorine atom and a bromine atom. The present invention will be explained in more detail below using Examples. Example 1 Structural formula below 20.4g of the compound shown and 3-cyano-4-
7.5 g of methyl-6-hydroxy-2-pyridone in 150 ml of N-methylpyrrolidone, 6.9 g of potassium carbonate
The mixture was heated at 160° C. for 1 hour in the presence of g. After cooling,
By diluting with methanol to remove the precipitate, washing with methanol and water, and drying, the following structural formula is obtained.

[expression] and

12.5 g of a compound represented by the formula (red crystals) was obtained. Further recrystallization purification was performed using N.N-dimethylformamide to obtain red crystals with a melting point of 320°C or higher. Elemental analysis value

[Table] Parent ion peak of mass spectrum m/e = 484
The compound obtained in this example exhibited extremely strong red fluorescence in N·N-dimethylformamide solution. Example 2 Structural formula below 20.1g of the compound shown and 3-cyano-4-
8.2 g of ethyl-6-hydroxy-2-pyridone was heated in 150 ml of quinoline at 160°C for 3 hours. After cooling, dilute with methanol to remove the precipitate, wash with methanol and water, and dry to obtain the following structural formula.

[expression] and

11.3 g of a compound represented by the formula (red crystals) was obtained. Further recrystallization purification with N.N-dimethylformamide gave red crystals with a melting point of 320°C or higher. Elemental analysis value

[Table] Parent ion peak of mass spectrum m/e = 494 The compound obtained in this example exhibited extremely strong red fluorescence in N·N-dimethylformamide solution. Example 3 Structural formula below 27.9g of the compound shown and 3-cyano-4-
7.5 g of methyl-6-hydroxy-2-pyridone in 150 ml of N-methylpyrrolidone, 6.9 g of potassium carbonate
The mixture was heated at 160° C. for 1 hour in the presence of g. After cooling,
The following structural formula was obtained by diluting with methanol to remove the precipitate, washing with methanol and water, and drying.

[expression] and

16.2 g of the compound represented by the formula (red crystals) was obtained. Further, the product was purified by recrystallization with N.N-dimethylformamide to obtain red crystals with a melting point of 320°C or higher. Elemental analysis value

[Table] Mass spectrum parent ion peak m/e = 546 The compound obtained in this example exhibited extremely strong red fluorescence in an N.N-dimethylformamide solution. Example 4 Structural formula below 17.2g of the compound shown and 3-cyano-4-
Add 7.5 g of methyl-6-hydroxy-2-pyridone to 150 ml of N-methylpyrrolidone in sodium carbonate.
Heated at 160° C. for 1 hour in the presence of 5.3 g. After cooling, dilute with methanol to remove the precipitate, wash with methanol and water, and dry to obtain the following structural formula.

[expression] and

10.6 g of a compound represented by the formula (red crystals) was obtained. Further, the product was purified by recrystallization with N.N-dimethylformamide to obtain red crystals with a melting point of 320°C or higher. Elemental analysis value

[Table] Parent ion peak of mass spectrum m/e = 422 The compound obtained in this example exhibited extremely strong red fluorescence in N·N-dimethylformamide solution. Example 5 The compounds shown in Table 1 were obtained by a method similar to the above example. As shown in the same table, each compound exhibited an extremely strong fluorescent color tone when dissolved in N.N-dimethylformamide.

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Claims (1)

[Claims] 1 General formula [Formula] or [Formula] (wherein R ¹ represents a hydrogen atom, an alkyl group, a trifluoromethyl group, an alkoxycarbonyl group, an alkoxycarbonylalkyl group, an aralkyl group, or a phenyl group; , R ² is an alkoxycarbonyl group that may have a substituent, a cyclohexyloxycarbonyl group, a tetrahydrofurfuryloxycarbonyl group, an aryloxycarbonyl group,
It represents a benzyloxycarbonyl group, an acyl group, a cyano group, or a carbamoyl group which may have a substituent, and R ³ represents a lower alkyl group. ) pyrazoloazaxanthenoisoquinolinones.