JPS5949943B2 - Manufacturing method for indoline dyes - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing indoline dyes.

More specifically, the present invention is based on the general formula [I] □IH-c□-- (wherein R1, R2 and R3 each represent a lower alkyl group, and R4 and R° each represent a hydrogen atom, a lower alkyl group, lower alkoxyalkyl group, lower alkoxyalkoxyalkyl group, aralkyl group, aryloxy lower alkyl group, halogeno lower alkyl group, cyano lower alkyl group, cycloalkyl group, alkoxycarbonyl lower alkyl group, acyloxy lower alkyl group, hydroxy lower alkyl group group, an amino lower alkyl group, a substituted amino lower alkyl group, or a phenyl group which may have a halogen atom, a lower alkyl group, or a lower alkoxy group as a substituent, and R5 is a cyano group, a carbamoyl group, or a lower alkoxycarbonyl group. shows.

The purpose of this invention is to industrially advantageously produce a novel indoline dye represented by However, this purpose, according to the present invention, is obtained by formula [0] (wherein Rl, R2 and R3 have the same meanings as in the above general formula [1]).

) and the general formula [button (in the formula, R4, R5
and R6 have the same meaning as in the general formula [1] above.

) is achieved by condensation with pyridones represented by

To explain the present invention in more detail, Rl, R2 and R3 in the above general formula [1] are each a methyl group, an ethyl group, a linear or branched propyl group, a butyl group, a pentyl group, Examples include lower alkyl groups such as hexyl, and R4 and R6 each include a methyl group, an ethyl group, a linear or branched propyl group, a butyl group, a pentyl group, and a hexyl group in addition to the hydrogen atom. Lower alkyl groups such as; lower alkoxyalkyl groups such as methoxyethyl and ethoxypropyl groups; lower alkoxyalkoxyalkyl groups such as methoxyethoxyethyl and ethoxyethoxyethyl groups: benzyl, methylbenzyl and methoxybenzyl groups , chlorobenzyl group, phenethyl group, aralkyl group such as chlorophenethyl group; aryloxy lower alkyl group such as phenoxyethyl group, methylphenoxyethyl group, methoxyphenoxyethyl group; halogen group such as chloroethyl group, promoethyl group Lower alkyl group; cyano lower alkyl group such as cyanoethyl group; cycloalkyl group such as cyclohexyl group; alkoxycarbonyl lower alkyl group such as methoxycarbonylethyl group, methoxycarbonylmethyl group: acetyloxyethyl group, benzoyloxyethyl group Acyloxy lower alkyl group such as; hydroxy lower alkyl group such as hydroxyethyl group; amino lower alkyl group such as aminoethyl group, methylaminoethyl group, diethylaminoethyl group, benzoylaminoethyl group, ethoxycarbonylaminoethyl group, A substituted amino lower alkyl group such as an ethylsulfonylaminoethyl group or a morpholinomethyl group; a phenyl group; Examples of R5 include cyano groups; carbamoyl groups; lower alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups.

In order to produce the indoline dye represented by the general formula [1] according to the method of the present invention, first the indoline dye represented by the general formula [l]
A compound represented by the above general formula [ ] in at least an equivalent amount
This is carried out by heating the pyridones represented by the following formula in acetic anhydride at a temperature of 60° C. to the boiling point, preferably 10° C. to the boiling point, for 2 to 10 hours.

At this time, the reaction can be made to proceed smoothly by adding a basic compound such as sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate.

After the reaction is complete, the reaction product often precipitates as crystals, but if it is in a dissolved state, the reaction product can be precipitated by adding a solvent with low dissolving power to the target reaction product. can be done.

By filtering and washing these precipitates, the compound represented by the above general formula [I], which is the object of the present invention, can be obtained with high purity and high yield.

The novel indoline dye represented by the general formula [I] obtained by the method of the present invention is a red fluorescent dye that can be used to make various organic media, synthetic fibers, plastics and other organic materials fluorescent. A dye that can be colored bright red,
Very useful as a pigment. Hereinafter, the method of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

Example 11,3,3-trimethyl-2-(formylmethylene)indoline 20.1f1 and 3-cyano-1,4
-dimethyl-6-hydroxy-2-pyridone16.
4 da was added to 100 ml of acetic anhydride, stirred under reflux for 3 hours, cooled to room temperature, and the precipitated crystals were collected, washed with water, and dried to obtain an indoline dye 31.2f1 (represented by the following structural formula). A theoretical yield of 90%) was obtained.

This product is a dark red crystal with a melting point of 320-322°C, and the elemental analysis results are as shown below, which agreed well with the calculated values.

When polyester fibers were dyed using this dye by a high-temperature dyeing method, a dyed fabric with bright fluorescent red color was obtained.

Example 2 1,3,3-Tirimethyl-2-(formylmethylene)indoline 20.1f1) 15.0g of 3-cyano-6-hydroxy-4-methyl-2-pyridone and 20f of sodium acetate (anhydrous) were dissolved in acetic anhydride. 150 go plus 10
After stirring at 0 to 110°C for 4 hours, it was cooled to room temperature, the precipitated crystals were collected by filtration, washed with water, and dried to obtain 32.6fI (theoretical yield: 98%) of an indoline dye represented by the following structural formula. Ta.

This product is a dark red crystal with a melting point of 338-340°C, and the elemental analysis results are as shown below, which agreed well with the calculated values.

When polyester fibers were dyed using this dye by a high-temperature dyeing method, a dyed fabric with bright fluorescent red color was obtained.

Furthermore, when polystyrene resin was colored using this dye, a bright red polystyrene resin with excellent light fastness was obtained. Example 3 1,3,3-trimethyl-2-(formylmethylene)
Indoline 20.1g, 3-cyano-6-hydroxy-
l-(3'-methoxypropyl)-4 monomethyl-2-pyridone 22.2 fI and potassium carbonate (anhydrous)
3.59 was added to 120 ml of acetic anhydride, stirred under reflux for 4 hours, cooled to room temperature, collected a lot of precipitated crystals, washed with water, and dried to obtain 39.2f of an indoline dye represented by the following structural formula. (Theoretical yield: 97%).

This dye is a dark red crystal with a melting point of 270-272°C.
The elemental analysis results are as shown below, and were in good agreement with the calculated values.

When polyester fibers were dyed using this dye by a high-temperature dyeing method, a dyed fabric with bright fluorescent red color was obtained.

Example 4 1,3,3-trimethyl-2-(formylmethylene)indoline 20.1f13-cyano-1-ethyl-6-hydroxy-4-methyl-2-pyridone 17.8f! and 2.5 f of potassium acetate were added to 120 d of acetic anhydride, stirred under reflux for 8 hours, cooled to room temperature, separated from the precipitated crystals, washed with water, and dried. .29 (theoretical yield 92%) was obtained.

This dye is a dark red crystal with a melting point of 284-286°C.
The elemental analysis results are as shown below, and were in good agreement with the calculated values.

When polyester fibers were dyed using this dye by a high-temperature dyeing method, a dyed fabric with bright fluorescent red color was obtained.

Example 5 1,3,3-trimethyl-2-(formylmethylene)indoline 20.1f11-benzyl-3-cyano-6-
24.0f of hydroxy-4-methyl-2-pyridone and 25y of sodium carbonate (anhydrous) were added to 140ml of acetic anhydride.
In addition, the indoline dye 41.5f (theoretical yield 98%) represented by the following structural formula was obtained by stirring under reflux for 4 hours, cooling to room temperature, filtering out the precipitated crystals, washing with water, and drying. Obtained.

This dye is a dark red crystal with a melting point of 249 to 252°C, and the elemental analysis results, as shown below, were in good agreement with the calculated values.

When polyester fibers were dyed using this dye by a high-temperature dyeing method, a dyed fabric with bright fluorescent red color was obtained.

Example 6 1,3,3-trimethyl-2-(formylmethylene)indoline 20.1f13-cyano-6-hydroxy-4
- 22.6 g of methyl-1-phenyl-2-pyridone and 2 ml of pyridine were added to 130 g of acetic anhydride, and under reflux
After stirring for an hour, it was cooled to room temperature, and the precipitated crystals were collected by filtration.
By washing with water and drying, an indoline dye 38.4f (theoretical yield: 94%) represented by the following structural formula was obtained.

This dye is a dark red crystal with a melting point of 315-316°C, and the elemental analysis results are as follows, which agreed well with the calculated values.

In addition, when polyester fibers were dyed using this dye by a high temperature dyeing method, a dyed cloth with bright fluorescent red color was obtained.

Example 7 Indoline dyes shown in Table 1 below were obtained by operating methods similar to those of the above-mentioned Examples.

The table also shows the color tones of dyed fabrics obtained when polyester fibers were dyed by the high temperature dyeing method using the obtained dyes. Example 8 Indoline dyes shown in Table 2 below were obtained by operating methods similar to those of the above-mentioned Examples.

Claims (1)

[Claims] 1 General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc.▼...[II] (In the formula, R^1, R^2 and R^3 each represent a lower alkyl group. ) Compounds represented by the general formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. , lower alkoxyalkyl group, lower alkoxyalkoxyalkyl group, aralkyl group, aryloxy lower alkyl group,
Halogeno lower alkyl group, cyano lower alkyl group, cycloalkyl group, alkoxycarbonyl lower alkyl group,
Represents an acyloxy lower alkyl group, a hydroxy lower alkyl group, an amino lower alkyl group, a substituted amino lower alkyl group, or a phenyl group which may have a halogen atom, lower alkyl group or lower alkoxy group as a substituent, and R^5 is Indicates a cyano group, carbamoyl group or lower alkoxycarbonyl group. ) is a general formula characterized by condensation with pyridones [I]▲There are mathematical formulas, chemical formulas, tables, etc.▼
... [I] (In the formula, R^1, R^2, R^3, R^
4, R^5 and R^6 are the general formula [II] or [I
II] has the same meaning. ) A method for producing indoline dyes.