KR900004222B1 - Process for preparing reactive disazo dye - Google Patents

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Description

Process for preparing reactive disazo dye

The present invention relates to a process for the preparation of new reactive disazo dyes covalently bonded with cellulose fibers.

In particular, the present invention relates to a process for preparing a new disazo-type reactive dye of the following general formula (I), which has two different reactive groups, has a high adsorption and fixation rate and excellent fastness.

Where S is SO ₃ H or a metal salt thereof: R ₁ and R ₂ are H, Cl or CH ₃ R ₃ is H, CH ₃ or COOH; R ₄ is H, OH, CH ₃ , OCH ₃ , SO ₃ H or COOH; R ₅ is H, NHCOCH ₃ , NHCONH ₂ , NH ₂ , COOH, SO ₃ H or CH ₃ ; R ₆ and R are H, CH ₃ , OCH ₃ , COOH, SO ₃ H, Cl Or OH; Z is a vinyl group or —CH ₂ CH ₂ —X; and X is a substituent capable of being removed by alkali to form a vinyl group; and Y is H or SO ₃ H.

The new reactive dye of the general formula (I) according to the present invention is colored with cellulose and becomes bright yellow. The conventional yellow reactive dyes having different reactive groups are mainly monoazo dyes. Examples of the compound having the same structure include:

Although the yellow dye has a light color, the depth of the color is weak, and dark yellow is not obtained even when a large amount of dye is added, and since it is poorly mixed with other dyes, it is not evaluated as a practical dye. .

As a darker yellow reactive dye, a dye such as the following structural formula is used.

The above monoazo compound containing 2-naphthylamine-polysulfonic acid compounds as a diazo component is one of the dyes currently used in terms of excellent tackiness and dark yellow color, but is generally difficult to wash and wash. Pollution is caused at the time, especially since the yield of the dye is low compared to the input of expensive raw materials, the cost is high, which is a disadvantage even if economical.

Accordingly, the present inventors have conducted extensive and in-depth research to develop a yellow dye having a bright yellow color with a dark yellow color and excellent blendability with other reactive dyes as well as economical formula. Invented the new disazo type yellow dye represented.

The new yellow dye of general formula (I) according to the present invention has a change in dyeing conditions, namely jade, dyeing temperature and amount of dyes, in addition to being bright in color, having excellent adsorption and fixing properties, and excellent blendability with other dyes. It shows a stable result even in the change of the back, shows excellent reproducibility, and has the strength that pollution problem does not occur at all when washing the steel easily.

In addition, the compound according to the present invention is excellent in all the printing properties, in particular excellent effect in various discharges (discharge), and has excellent conditions that can replace the existing yellow-based reactive dyes as a whole.

Compounds of the general formula (I) according to the present invention may be prepared by converting the compounds of the general formula (II) to 1,3-phenylenediamine-4-sulfonic acid or 1,3-phenylenediamine-4,6-disulfonic acid and 2,4 A compound of formula (III) was prepared by coupling with a diazo compound of a condensate with 6-trichloro-1,3,5-triazine, and separately diazotized a compound of formula (IV). The azo compound of formula (VI) may be prepared by carrying out a coupling reaction with the compound of (V), followed by condensation of the compound of formula (III) and (VI) above:

(S, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , X, Y and Z are as defined above).

The method of the present invention is described in detail as follows. That is, in the first batch, the condensate of 1,3-phenylenediamine-4-sulfonic acid and 2,4,6-trichloro-1,3,5-triazine is diazotized at 5 ° C. or lower, and then The coupling reaction is carried out under a weak alkalinity with the pyrazolone compound of formula (II). The azo compound obtained at this time is the same as the structure of general formula (IV). In addition, in the second batch, the vinylsulfone diazo component of formula (IV) is diazotized and then coupled at a temperature of 5-15 ° C. and a pH in the range of 3-5 using a coupling component such as formula (V). Perform ring reaction. The azo compound obtained at this time is the same as that of general formula (VI).

After completion of each batch of guffling reactions, the second condensation reaction is carried out at the temperature range of 30-60 ° C., preferably 40-50 ° C., for the two compounds of general formula (III) and general formula (Vl). . At this time, the condensation reaction is checked by TLC (thin layer chromatography) or other instrumental analysis equipment. When the condensation reaction is completed, salting and filtration are performed with salt or potassium chloride, and the resulting cake is dried under reduced pressure at a temperature in the range of 40-80 ° C. To give the final compound represented by formula (I).

In addition, the compound of general formula (I) can also be manufactured by the following method. That is, the compound of formula (VI) and cyanuric chloride are condensed at 5 ° C. or lower, and then the reaction product thereof is subjected to a condensation reaction with a compound of formula (VII) at a temperature of 40-50 ° C. to obtain a final product. Obtain the compound of formula (I):

Where S, R ₁ , R ₂ , R ₃ and Y are as defined above.

Examples of the compound of formula (II) used in the present invention include 1- (4'-sulfophenyl) -3-methyl-5-pyrazolone, 1- (4'-sulfophenyl) -3-carboxy-5- Pyrazolone, 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-pyrazolone and 1- (2', 5'-disulfophenyl) -3-methyl-5-pyrazolone Can be mentioned.

Further examples of the compound of the general formula (IV) used in the present invention are as follows: 1-amino-2-methyl-5-β-sulfato ethylsulfone, 1-amino-4-methyl-3-β- Sulfate ethyl sulfone, 1-amino-2-sulfophenyl-5-β-sulfato ethyl sulfone, 1-amino-2-sulfophenyl-4-β-sulfatoethyl sulfone, 1-amino-2- Carboxyphenyl-4-β-sulfato ethylsulfone, 1-amino-phenyl-4-β-sulfato ethylsulfone, 1-amino-phenyl-3-β-sulfate ethylsulfone, 1-amino-2-meth Methoxyphenyl-5-β-sulfato ethylsulfone, 1-amino-4-methoxyphenyl-3-sulfato ethylsulfone, 1-amino-2,5-dimethoxyphenyl-4-sulfato ethyl Sulfone, 1-amino-2-methoxy-5-methylphenyl-4-sulfate ethylsulfone, 1-amino-2-chlorophenyl-4-sulfato ethylsulfone and 1-amino-4-chlorophenyl-3-sul Peytoethylsulfone.

And examples of the compound used as the compound of general formula (V) are as follows: 3-amino-acet anilide, 3-aminophenyl-urea, 1,3-phenylenediamine-4-sulfonic acid, para-cresidine , 2,5-dimethylaniline, 2,5-dimethoxyaniline and 3-amino toluic acid.

Hereinafter, the present invention will be described in more detail with reference to the following examples, in which all parts refer to parts by weight.

Example 1

(One). 18.8 parts of 1,3-phenylenediamine-4-sulfonic acid are neutralized and dissolved with 200 parts of water and an appropriate amount of alkaline agent. 18.5 parts of cyanuric chloride are dissolved in 100 parts of acetone and dispersed while stirring with 200 parts of ice water. After adding the neutralizing solution to the dispersion, the pH is slowly lowered to neutral at 5 ° C or lower. When condensation is completed, add a solution of 7.3 parts of sodium acetate and 20 parts of water, add 50 parts of ice, and add 30 parts of concentrated HCL to carry out the diazotization reaction. Meanwhile, 28.4 parts of 1- (4'-sulfophenyl) -3-carboxy-5-pyrazolone compound, 200 parts of water, and neutralizing and dissolving with a predetermined alkali agent are added, and then 200 parts of sodium carbonate are added. The diazo solution is slowly added to the pyrazolone solution while the pH is kept in the range of 8-9.

(2). 36.1 parts of 1-amino-2-sulfophenyl-4-sulfato ethyl sulfone compound are diazotized to 7.5 parts of sodium acetate at 5 ° C. or lower, and then excess acetic acid is removed. Meanwhile, a solution of 15 parts of m-amino-acetanilide and 200 parts of water is stocked in a diazo solution. Slowly add 15 parts of sodium acetate to raise the pH to 4. When the coupling reaction is completed, salt is added to 20% of the liquid salt, salted and filtered to obtain a cake.

(3). After adding a small amount of hydrochloric acid to the coupling reaction liquid in (1) above to adjust the pH to 6.0, the dispersion of the cake of (2) above and 500 ml of water is added to the reaction liquid of (1). The condensation reaction is carried out while the temperature is raised to 45 ° C. and the free acid is added with sodium bicarbonate to maintain a pH in the range of 5-6. After the condensation was completed, NaCl was added to remove the crystals, and the obtained cake was filtered and dried under reduced pressure at 60 ° C. to obtain a dye of the following structural formula (160 parts of drying amount):

Dyeing the dye on the cotton showed a high concentration of yellow with excellent fastness.

Example 2-10

In Example 1 (2), instead of 1-amino-2-sulfophenyl-4-sulfatoethylsulfone, compound A shown in the following table was used, and instead of m-amino-acet anilaido, The same procedure as in Example 1 was repeated except that Compound B was used.

Example 11

(One). Use of l- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-5-pyrazolone compound instead of 1- (4'-sulfophenyl) -3-carboxy-5-pyrazolone Except for the same procedure as in Example 1- (1), the intermediate compound of the following structural formula was obtained.

(2). After diazotizing 28.1 parts of 1-amino-3-β-sulfatoedylsulfone compound with 7.5 parts of sodium acetate, the solution was neutralized with 18.8 parts of 1,3-diamino phenylene-4-sulfonic acid and 200 parts of water. The diazolation solution was added to the stock and the coupling reaction was performed at a pH in the range of 3-5.

(3). After each coupling reaction was completed, the two solutions of (1) and (2) were mixed to perform condensation at a temperature of 45 ° C. At this time, the falling pH value is maintained in the range of 5-6 using a sodium bicarbonate solution.

When the reaction is completed, KCl is added to precipitate a crystal and filtered. The compound thus obtained has a structure in the form of the free acid as follows:

Example 12-19

The same procedure as in Example 11 was carried out except that the compound shown in the following table was used instead of the 1-amino-4-β-sulfatoethylsulfone compound to obtain a yellow dye having the same effect.

Example 20

Example 1 except that 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-pyrazolone was used instead of 1- (4'-sulfophenyl) -3-carboxypyrazolone The same procedure was followed to obtain a dye of the following structure in free acid form:

Example 21

Example except that 1- (4'-sulfophenyl) -3-carboxy-pyrazolone was used instead of 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-pyrazolone The same method as in 11 was carried out to obtain a dye of the following structural formula:

Example 22

The same procedure as in Example 1 was carried out except that 26.8 parts of 1,3-phenylenediamine-4,6-disulfonic acid was used instead of 18.8 parts of 1,3-phenylenediamine-4-sulfonic acid in the form of a free acid. The dye of the following structural formula was obtained:

The above dyes had excellent solubility and were dyed on cotton to give a clear yellow dyeing with good fastnesses.

Claims (1)

The compound of formula (II) was substituted with 1,3-phenylenediamine-4-sulfonic acid or 1,3-phenylenediamine-4,6-disulfonic acid and 2,4,6-trichloro-1,3,5- The compound of formula (III) was prepared by coupling with a diazo compound of a condensate with triazine, and after diazotizing the compound of formula (IV), a coupling reaction was performed with a compound of formula (V). A method of preparing a reactive disazo dye represented by the general formula (I) by preparing a dizo compound of the general formula (VI) and then condensing the compounds of the general formulas (III) and (IV) above:

Wherein S is SO ₃ H or a metal salt thereof: R ₁ and R ₂ are H, Cl or CH ₃ R ₃ is H, CH ₃ or COOH; R ₄ is H, OH, CH ₃ , OCH ₃ , SO ₃ H or COOH; R ₅ is H, NHCQCH ₃ , NHCONH ₂ , NH ₂ , SO ₃ H, COOH or CH ₃ R ₆ and R ₇ are H, CH ₃ , OCH ₃ , COOH, SO ₃ H, Cl Or OH; Z is a vinyl group or -CH ₂ CH ₂ -X; X is a substituent which can be removed by alkali to form a vinyl group; and Y is H or SO ₃ H.