KR100578318B1 - Process for preparing disperse dyes - Google Patents

Abstract

The present invention relates to a process for producing disperse dyes. More specifically, the present invention provides a process for producing a disperse dye having a structure represented by the following general formula (1) and general formula (2) by reacting a compound having an anthraquinone structure with diphenyl carbonate of the general formula (5).

X is an oxygen atom or a sulfur atom, R ₁ is C ₂ -C ₆ alkylene, R ₂ is C ₂ -C ₆ alkylene, and n is 1 or 2.

According to the present invention, the dispersion dyes of the general formula (1) and the general formula (2) can be produced in a high yield with a safer and simpler process than the conventional technique.

Disperse dyes, anthraquinone, carbonates, diphenyl carbonate

Description

PROCESS FOR PREPARING DISPERSE DYES [0002]

Disperse dyes are dyes which are insoluble in water and which are mainly used for dyeing acetate, nylon and polyester fibers in a state of being dispersed in water. That is, the disperse dye is a fine powder that does not dissolve in water and disperses it in a colloidal state in water using a dispersant such as a surfactant to dye the fiber. These include azo, anthraquinone, azomethine, and nitro-based dyes, which are dominated by azo and anthraquinone dyes.

The present invention relates to a process for producing an anthraquinone disperse dye represented by the following general formula (1) and general formula (2). More particularly, the present invention is characterized by providing a method of preparing a dispersion dye having the following structure by reacting a compound having an anthraquinone structure with diphenyl carbonate, respectively, as compared with the conventional method.

X is an oxygen atom or a sulfur atom, R ₁ is C ₂ -C ₆ alkylene, R ₂ is C ₂ -C ₆ alkylene, and n is 1 or 2.

Disperse dyes represented by the general formulas (1) and (2) were first disclosed in U.S. Patent No. 3,689,510 (1972), and US Pat. No. 3,767,681 (1973) and U.S. Patent No. 3,769,305 (1) and the general formula (2) in US Pat. No. 3,803,168 (1974), US Pat. No. 3,806,524 (1974) and US Pat. No. 4,804,767 , It is described that they are synthesized by using a compound represented by the following general formula (6), which is a compound having a haloformate structure, in common to an anthraquinone structure compound, although their respective production conditions are different.

However, since the phenyl chloroformate of the general formula (6) has a very high reactivity, there is a difficulty in requiring an anhydrous environment during storage and use, and since an acidosis occurs in the process of synthesizing a disperse dye, The base should be used in an equivalent or equivalent amount as an acid inhibitor. And also has the disadvantage of causing discoloration by reacting with the aromatic amine of the dye main body due to unreacted remnants after the reaction.

The present invention uses a diphenyl carbonate of the general formula (5) as a method for solving the above problems, and it is an object of the present invention to provide an acidic vapor And a desired compound can be obtained safely without occurrence of the above-mentioned problems.

In addition, since the synthesis by-products can be easily removed by reprecipitation and washing with methanol, a dispersion dye can be obtained by a simpler process than the conventional production method. In addition, a relatively high yield can be obtained as compared with the conventional production method.

It is an object of the present invention to overcome the disadvantages of the conventional production method without special equipment through modification of the synthetic raw materials and the manufacturing method and to provide a dispersion dye of the general formula (1) and the general formula (2) And to provide a method that can be obtained.

In order to accomplish the above object, the present invention provides a process for producing an anthraquinone compound represented by the general formula (1) by reacting an anthraquinone compound of the general formula (3) and a diphenyl carbonate of the general formula (5) ) And a disperse dye represented by the general formula (2).

X is an oxygen atom or a sulfur atom, R ₁ is C ₂ -C ₆ alkylene, R ₂ is C ₂ -C ₆ alkylene, and n is 1 or 2.

(1) and (2) by reacting an anthraquinone compound represented by the general formula (3) and an anthraquinone compound represented by the general formula (4) ≪ / RTI > In the present invention, by using the diphenyl carbonate of formula (5) and an alkali catalyst in place of the phenyl chloroformate of the above-mentioned general formula (6), the stability and easiness of the process are ensured and only the agitator A high yield of disperse dye synthesis has become possible.

First, an anthraquinone-based material having a structure represented by the general formula (3) or (4) and a diphenyl carbonate represented by the general formula (5) To 2 equivalents, dissolved in an appropriate solvent, heated to an appropriate temperature and stirred. Subsequently, a catalyst suitable for use in the condensation reaction is added and stirred, and the reaction solution is poured into methanol to precipitate the dye crystals of the formula (1) or (2).

The solvent used in the present invention can dissolve reactants well and has affinity with alcohols such as methanol. The solvent is preferably a ketone such as acetone or 2-butanone, an ether such as diethyl ether or dioxane Can be used.

In addition, the catalyst used in the present invention is prepared by using hydroxides of lithium hydroxide, sodium hydroxide, potassium hydroxide and the like and carbonates such as sodium carbonate, potassium carbonate and cesium carbonate in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight do.

The reaction temperature is preferably from 50 to 110 ° C, and preferably from 70 to 90 ° C, depending on the solvent used.

The structure of the finally synthesized disperse dye was confirmed by nuclear magnetic resonance spectrometer and infrared spectrometer. The purity was confirmed by ultraviolet spectrometer and high performance liquid chromatography.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following examples.

Example 1

A round bottom flask was equipped with a stirrer, and then 200 g of 1-amino-4-hydroxy-2-b-hydroxyethoxyanthraquinone and 280 g of diphenyl carbonate were mixed with 800 g of 1,4-dioxane, And stirred. 10 g of potassium hydroxide is added in powder form, and the mixture is stirred at 80 to 85 ° C for 3 hours. The reaction solution is poured into 3000 g of methanol to precipitate and then left at room temperature for about 1 hour. The resulting dye crystals are filtered off under reduced pressure and washed twice with an aqueous solution of 2000 g. Washed once with 500 g of methanol and dried to obtain 249.2 g of a bright red dye. The yield is 89.0%.

Bromo-potassium pellets were prepared from the above compounds and subjected to infrared spectroscopic analysis under the conditions of a number of injections of 16 times and a resolution of 4 cm ^-1 at room temperature using an infrared spectrometer (FT / IR-480 plus, JASCO). ¹ H-NMR (VARIAN 200 MHz, VARIAN) was used for the nuclear magnetic resonance spectroscopy and tetramethylsilane was used as the solvent for the CDCl ₃ reference material.

IR (KBr): v _max = 1762 cm ^-1 (-O- CO- O-)

^{1 H-NMR: d (ppm} ): 4.39 (2H, t, -OCH 2 -), 4.75 (2H, t, -CH 2 -OCO 2 -), 6.59 (1H, s, ArH), 7.15 ~ 7.50 ( (2H, m, ArH), 8.40 (2H, m, ArH)

UV: lmax = 511.00 nm (400 nm to 600 nm)

Comparative Example 1

After placing the stirrer in a round bottom flask, 10 g of 1-amino-4-hydroxy-2-b-hydroxyethoxyanthraquinone is dispersed in 40 g of toluene and 3.4 g of pyridine is added as an acid inhibitor. The mixed solution was sufficiently stirred at 70 ° C, and 10.5 g of phenyl chloroformate was diluted in 10 g of toluene and slowly added. When the introduction of the phenyl chloroformate is completed, the reaction solution is stirred at 70 ° C for 1 hour. The reaction solution was cooled to 20 占 폚, precipitated in 300 g of methanol, and washed with water and methanol to obtain a red dye in a state containing a large amount of yellow adverse reaction products. This mixture was purified by liquid chromatography to obtain 11.0 g of a red dye. The yield is 79%.

Comparative Example 2

After placing the stirrer in a round bottom flask, 10 g of 1-amino-4-hydroxy-2-b-hydroxyethoxyanthraquinone is dispersed in 40 g of toluene and 12.8 g of pyridine is added as an acid inhibitor. The mixed solution was sufficiently stirred at 70 ° C, and 7.9 g of phenyl chloroformate was diluted in 10 g of toluene and slowly added. When the introduction of the phenyl chloroformate is completed, the reaction solution is stirred at 70 占 폚 for 2 hours to 3 hours. The reaction solution was cooled to 20 DEG C and precipitated in 300 g of methanol. The precipitate was filtered and washed with water and methanol to obtain 10.7 g of a red dye. The yield is 76%.

Examples 2 to 8

A dye was prepared in the same manner as in Example 1 except that the anthraquinone compound of Table 1 and diphenyl carbonate were used instead of 1-amino-4-hydroxy-2-b-hydroxyethoxyanthraquinone of Example 1 Were synthesized.

Example Anthraquinone compound color yield(%) 2

Red 88% 3

Red 88% 4

Red 89% 5

Purple 89% 6

Purple 88% 7

Red 88% 8

blue 87%

As can be seen from the above Examples and Comparative Examples, by using a diphenyl carbonate of the general formula (5) and an alkaline base which can be easily removed even by a simple rinse as a catalyst, a desired process And the synthesis by-products can be easily removed only by reprecipitation and washing with methanol, so that the dispersion dye can be obtained in a high yield with a simpler process than the conventional production method.

As described above, the present invention can provide a method for obtaining a dispersion dye at a high yield with a safer and simpler process.

Claims (5)

A process for producing a disperse dye, which comprises reacting an anthraquinone compound represented by the following structural formula (3) with a diphenyl carbonate represented by the following structural formula (5) to prepare a disperse dye represented by the following structural formula (1).

(Wherein X is an oxygen atom or a sulfur atom, R ₁ is C ₂ -C ₆ alkylene or thioalkylene, and n is 1 or 2). Wherein the anthraquinone compound represented by the following structural formula (4) and the diphenyl carbonate represented by the following structural formula (5) are reacted to prepare a disperse dye represented by the following structural formula (2).

(Wherein R ₂ is C ₂ -C ₆ alkylene, and n is 1 or 2). The method according to claim 1 or 2, wherein the anthraquinone compound represented by the structural formula (3) or (4) and the diphenyl carbonate represented by the structural formula (5) are mixed and dissolved in a solvent; Heating and stirring; Adding a catalyst used for the condensation reaction and stirring to obtain a reaction solution; The reaction solution is poured into methanol to precipitate to prepare a disperse dye represented by the structural formula (1) or (2). The method for producing a dispersion dye according to claim 3, wherein the solvent is selected from a ketone compound or an ether compound. The method for producing a dispersion dye according to claim 3, wherein the catalyst is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or cesium carbonate.