JPS5950260B2 - Manufacturing method of dioxazine compound - Google Patents

Description

[Detailed description of the invention] The present invention relates to an improved method for producing dioxazine compounds.

More specifically, the general formula (■) of the present invention H-Ar-NHON
A compound represented by H-Ar-H (■) (wherein Ar is an aromatic residue with or without a substituent, and Y represents a halogen atom, an acylamino group, or an acyloxy group) is added to a polar aprotic solvent. A method for producing a dioxazine compound represented by the general formula (202) (1) (wherein Ar and Y have the above meanings), characterized by heating to 100-200 ° C. It is.

The compound represented by the general formula (I) is important as a raw material compound for dyes, especially pigments. Conventionally, the compound represented by the general formula (■) was dissolved in an inert solvent such as dichlorobenzene, trichlorobenzene, or nitrobenzene. , is synthesized by heating to 0-200°C in the presence of an acid halide. The disadvantages of this method are insufficient yields,
Among the pigment properties of the obtained dioxazine compound, it is inferior in terms of bleed resistance and solvent resistance.

As a result of intensive studies to improve the above drawbacks, the present inventors used a polar aprotic solvent as a reaction solvent, and
It has been found that the objective can be achieved by heating at 0-200°C. Compared to conventional methods, the method of the present invention has a shorter reaction time, higher yield, and higher purity of the obtained product, and when it is made into a pigment, its solvent resistance and bleed resistance are is extremely excellent.

In the present invention, examples of the compound represented by the general formula () include the following compounds.

Examples of polar aprotic solvents include the following compounds.

Dimethylformamide, diethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, tetramethylurea, sulfolane, hexamethylphosphoramide, pyridine, picoline, methylquinoline, quinoline These can be used alone or in combination, It can also be used in combination with other solvents.

Among these, quinoline is particularly preferred. Specifically, the present invention can be implemented, for example, as follows. A diimide compound of general formula () in a polar aprotic solvent is added at 100-200°C, preferably 140°C.
Heat to 170°C. At this time, preferably a halide is added. Examples of the halides include benzenesulfonyl chloride, o- or p-toluenesulfonyl chloride, benzoyl chloride, thionyl chloride, and chloranil. The amount added is at most 2 molar ratio to the diimide compound. The addition of halides is carried out before or after raising the temperature, requiring a short or long period of time. In this reaction, an inert gas such as nitrogen or carbon dioxide may be passed through. After completion of the reaction, and optionally after neutralization, it may be separated by means such as passing through, or it may be transferred to a pigment formation step such as atomization without separation.

The compound of general formula (1) obtained in this way has excellent yield and purity, and the pigment obtained by atomizing it using this compound is superior to conventional ones in terms of bleed resistance and solvent resistance. It is superior to that obtained by the law. Furthermore, dyes of excellent quality can also be obtained through processes such as sulfonation. Next, the present invention will be explained with reference to examples.

In the text, parts represent parts by weight. Example 1 25 parts of the compound shown in (1) above and 150 parts of quinoline were mixed, and 15 parts of the compound shown in (1) above were mixed, and nitrogen was slightly passed through the upper part of the reaction solution.
14.8 parts of benzenesulfonyl chloride is added dropwise over 1.5 hours at 0-160°C, and the mixture is kept at this temperature for 3 hours.

After the reaction is completed, it is cooled, and the crystals obtained are separated, washed with quinoline, then methanol and water, and dried. 23.0 parts of highly pure green crystals were obtained.

This product had the following structural formula based on elemental analysis and infrared absorption spectrum. Comparative Example 1 25 parts of the compound shown in (1) above and 250 parts of dichlorobenzene were mixed, and 1 part of benzenesulfonyl chloride was mixed at 160-170°C while nitrogen was slightly passed through the upper part of the reaction mixture.
4.8 parts were added dropwise over 1.5 hours and kept at this temperature for 6 hours.

It was then treated in the same manner as in Example 1. Example 1 with low purity
19 parts of a compound having the same structural formula was obtained. Reference example 1 Compound 2709 obtained in Example 1, sodium chloride 2
3009 and polyethylene glycol (molecular weight approximately 40
0) 4109 was placed in a Baker Perkins dispersion mixer having a capacity of 41 and the mixture was milled for 15 hours.

After completing the grinding, the mixture was stirred with 101 °C of warm water, then filtered to remove the polyethylene glycol and salt, and the washing was repeated several more times to obtain a cake of 8 °C.
Dry at 0-90°C. Pigmented purple compound 268
I got a 9. When the obtained pigment was subjected to a toluene solvent resistance test according to JISK-5101 (pigment test method), there was almost no coloration and it was found to be a cardner (▲2).

Furthermore, 1% of this pigment was added to a soft vinyl chloride compound containing 50% plasticizer, kneaded at 145°C to form a colored soft vinyl chloride sheet, and this colored sheet and a white sheet of soft vinyl chloride were layered at 100g/Cl? Under the load of L,
A bleed resistance test was conducted under the conditions of 80°C and 20°C. Bleed to the white sheet was extremely slight and did not overlap with the colored sheet. The color difference ΔE from the white sheet was 1.3. On the other hand, the compound of Comparative Example 1 synthesized using dichlorobenzene as an inert solvent was converted into a pigment under the above conditions, and in the solvent resistance test under the same conditions, it was markedly colored as a cardner ▲12. In the bleed resistance test of soft vinyl chloride, it was significantly colored and the color difference ΔE was 8.9. Example 2 In Example 1, benzenesulfonyl chloride 14.
16 parts of p-toluenesulfonyl chloride instead of 8 parts.
The compound of Example 1 was obtained in high yield by carrying out the same procedure except that 0 part was used.

Further, the same procedure as in Example 1 was carried out except that dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone were used instead of quinoline, and the compound of Example 1 was obtained in high yield in each case.

Example 3 25 parts of the compound (3) above and 300 parts of quinoline
Mix the parts and heat to 150-160 ml with a slight stream of nitrogen.
17 parts of p-toluenesulfonyl chloride was added dropwise at °C.
Heat at 165-170°C for 3 hours.

After the reaction is completed, the obtained crystals are distributed from house to house, washed and dried. High purity compound with the following structural formula (green crystal) 2
Got 2 copies. Example 4 25 parts of the compound (1) above, 30 parts of dimethylformamide
Mix 0 parts and add 140-15 while passing nitrogen slightly.
Add benzenesulfonyl chloride dropwise over 1.5 hours at 0°C and heat at 140-150°C for 3 hours.

Claims (1)

[Claims] 1 General formula ▲ Numerical formulas, chemical formulas, tables, etc. ) is heated to 100-200℃ in a polar aprotic solvent. There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (where Ar and Y have the above meanings) ) The method for producing the dioxazine compound shown in