JPS606755A - Production of azo dye - Google Patents

Abstract

PURPOSE:To produce an azo dye suitable for use as a reactive dye for dyeing cellulosic fiber materials, by diazotizing an aminonaphthalene compd., coupling the diazotized compd. with a coupling component and condensing the resulting azo compd. with cyanuric chloride and an aniline compd. CONSTITUTION:An aminonaphthalene compd. of formula II (wherein R is H, lower alkyl) is diazotized and coupled with a coupling component of formula III[wherein D is a residue of the coupling component (hydroxynaphthalene compd., pyrazolone compd., etc.)]. The resulting azo compd. of formula IV is condensed with cyanuric chloride and an aniline compd. of formula V or VI (wherein X1, X2 are each H, methyl, methoxy, sulfo group) in any order (when the aniline compd. of formula VI is used, the condensate is further esterified with sulfuric acid) to produce an azo dye of formula I in the free form.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an azo dye particularly suitable for reactive dyeing of cellulosic fiber materials.

It is well known that dyes having -3O2CH2CH20SO3H or monochlorotriazinyl groups are used as reactive dyes for dyeing textile materials. This type of dyeing gives dyeings with excellent wet fastness, light fastness and chlorine fastness in dyeing.
As a result of extensive research into methods for producing reactive dyes, the present invention has been completed.

That is, the present invention is based on the following general formula (I): RHNCH2 03H (4) (wherein R represents a hydrogen atom or a lower alkyl group)
) is diazotized and coupled with a coupling component represented by the general formula (Ill) HD (III) (wherein D represents a residue of the coupling component). an azo compound represented by the following general formula (IV) (wherein D and R have the above-mentioned meanings) and the following general formula (V) obtained by (representing a hydrogen atom, methyl group, methoxy group or sulfonic acid group) is condensed with cyanuric chloride in any order, and when the aniline compound represented by the general formula (■) is used, then sulfuric acid is used. Obtained by esterifying or condensing an amine naphthalene compound represented by general formula (n) and an aniline compound represented by general formula (ma) or (Vl) with chloride, anu, or chloride in any order The following general formula (■p OaH (wherein, Y represents a hydrogen atom or a sulfo group, R,
I, X2 have the meanings given above. ) is diazotized and coupled with a coupling component represented by general formula (III), and when an aniline compound represented by general formula 〇'l) is used, it is then sulfuric acid esterified. The following general formula (
I) Provided is a method for producing an azo dye represented by the formula (wherein D + R+ XI + X2 has the above-mentioned meaning).

Examples of the coupling component of general formula (III) include substituted or unsubstituted hydroxybenzene, aminobenzene, aminonaphthalene, hydroxynaphthalene, aminohydroxynaphthalene, and amide compounds.

Particularly preferred among these are the following general formulas (1) to I.
V).

(1) Hydroxynaphthalene compound O (in the formula, n represents 1.2 or 3) (it) Aminohydroxynaphthalene compound (in the formula, Aayl is an acyl group, such as argylcarbonyl, alkylsulfonyl, aryl) (represents carbonyl or arylsulfonyl) (+r++ pyrazolone compound (wherein A is a methyl group, a carboxyl group or a carbonamide group, B is a hydroxyl group or an amino group, and E is an alkylphenyl group having at least one sulfonic acid group) or a naphthyl group.) (1v) Pyridone compound (in the formula, K.G is a lower alkyl group, J is a carbonamide /S loken, sulfonic acid, cyano, hydrogen is a null As a specific example of general formula (++1) (representing a lefomethyl group), the following compound 11: can be cited.

l-Amino-2-sulfo-5-acetylaminobenzene, 2-amino-5,6- or 7-sulfonaphthalene, 2
-amino-5,7-disulfonaphthalene, 2-amino-
8.6-disulfonaphthalene, ■-amino-6 or 7
-Sulfonaphthalene, 1-amino-3-acetylaminobenzene, 1-amino-3-ureidobenzene, ■-amino-3-methyl-benzene, 1-amino-3-methyl-6-medoxybenzene, ■-amino-2.5 -dimethquinbenzene, 1-hydroxy-5-sulfonaphthalene, l-hydroxy-8,6-disulfonaphthalene, -hydroxy-8,7-disulfonaphthalene, l-hydroxy: 3.

7-disulfonaphthalene, ■-hydroxy-3,8-disulfonaphthalene, 1-hydroxy-4,6-disulfonaphthalene, 1-hydroxy-4,7-disulfonaphthalene + 1-hydroxy-4,8-disulfonaphthalene Naphthalene, l-hydroxy-8,5-disulfonaphthalene, 1-
Hydroxy-8-benz-r-ruamino-8,6-disulfonaphthalene, J-hydroxy-8-penzoylamino-3,5-disulfonaphthalene, ■-Hydroxy-8-
Ureido-8, 6-dinaphthalene, -Hydroxy-8-ureido-8,5-disulfonaphthalene, 1-hydroxy-8-acetylamino-3,6-disulfonaphthalene, l-hydroxy-8-acetylamino- 3,5-
Disulfonaphthalene, l-hydroxy-7-amino-3
-Sulfonaphthalene, l-hydroxy-7-phenylamino-8-sulfonaphthalene.

l-hydroxy-8-amino-3,6-disulfonaphthalene, ■-hydroxy-8-amino/-8,5-disulfonaphthalene, ■-hydroxy-7-amino-8,6-disulfonaphthalene, l-hydroxy- 6-amino-8-
Sulfonaphthalene, 1-hydroxy-6-amino-8,
5-disulfonaphthalene, l-(2'.

a', t is 4'-sulfophenyl)-3-methyl-pyrazolone-5,1-(2'-chloro-4' or 5'-sulfophenyl)-8-methylpyrazolone-5,
l -(2'-methyl-4fusulfophenyl)-3-
Methylpyrathrono5.1- (2'-methyl-4'-
5. Sulfophenyl)-3-carboxy-pyrazolono.
1-β-carboxyethyl-3 to carboxin-pyrazolone-5, l-C4', 8-disulfonaphthyl-(2)]
-]8-Methyl-pyrazolone-5■-(6', 7'-
Disulfonaphthyl T2+) -8-methyl-pyrazolone-5,1-(2'-chloro-5'-sulfophenyl)
-3-methyl-5-amino-pyrazole, l -(2'
-chloro-4'-sulfophenyl)-3-methyl-5-
Aminobi7so Jb, l (31 or 4'-sulfophenyl)-3-methyl-5-aminopyrazole, ■-carboxymethyl-8-methyl-pyrazolo/-5, ■-β-
Carboxyethyl-8-methylvilatulono 5.1-β
-Carboxyethyl-8-methyl-5-aminopyrazole, 1-(4'-sulfophenyl)-3-carboxy-pyrazolone-5,8-cyano-4-methyl-6-hydroxypyridone, l,4-dimethyl- 3-no-no-6-
Hydroxypyridone, ■-Ethyl-3-cyano-4-methyl-6-hydroxypyridone, 1-propyl-3-noano-4-methyl-6-hydroxypyridone, 8-aminocarbonyl-4-methyl-6-hydroxypyridone,
l,4-E) Methyl-3-aminocarbonyl-6-hydroxypyridone l-ethyl-8-aminocarbonyl-4
-Methyl-6-hydroxypyridone, -Propy-8-aminocarbonyl-4-methyl-6-monohydroxypyridone, 4-methyl-6-hydroxypyridone-3
-sulfonic acid, l,4-dimethyl-6-hydroxypyridone-8-nosulfonic acid, ■-ethyl-4-methyl-6-1hydroxypyridone-8-sulfonic acid, l-
Woprobyl-4-methyl-6-hydroxypyri t-8-sulfonic acid, 8-sulfomethyl-di-4-methyl-
6-hydroxypyridone, l.

4-dimethyl-8-sulfomethyl-6-hydroxypyridone, l-ethyl-8-sulfomethyl-4-methyl-6
-hydroxypyridone, -propyl-3-sulfomethyl-4-methyl-6-hydroxypyridone and 5-carboxylic acid amide substituted products thereof.

Examples of the aniline compound of general formula (V) include the following compounds.

1-Aminebenzene-2-1-3- or -4-β-sulfatoethylsulfone, 1-7′mino-4-methylbenzene-3-β-sulfatoethylsulfone, 1-diamino-4-methoxy Benzene-8-β-sulfonate, phytoethylsulfone, l-aminobenzene-4-β-sulfatoethylsulfono-2-sulfonic acid, [-aminobenzene-5-β-sulfatoethylsulfone-2-sulfonic acid , ■-amino-5-β-sulfatoethylsulbo/-2,4-disulfonic acid, 1-amino-2゜5-
Dimepon sibensene-4-β-sulfatoethylsulfane, ■-amino-2-methynebenzene ~ 5-β-sulfa; ethylnurpon, 1-amino-2-methoxy5-methylbenzene ~ 4-β - Sulfa l-x Tylsulfone In carrying out the method of the present invention, an aminonaphthalene compound represented by the general formula (formula) is diazotized, and this and the general formula (I
By coupling with a coupling component represented by ll), an azo compound represented by general formula ('IV) is obtained. The azo dye of general formula (I) can be obtained by firstly condensing cyanuric chloride with this azo compound (IV) and then secondarily condensing the aniline compound represented by general formula (V).

Alternatively, cyanuric chloride and a leraniline compound represented by the general formula <V) are primarily condensed, and then the general formula (ff)
The azo dye of general formula CI) can also be obtained by secondarily condensing an azo compound represented by An aniline compound is condensed with cyanuric chloride in any order to obtain a compound having the general formula (■゛)0sH (wherein R, X+, and Xz have the meanings given above). can be diazotized and coupled with a coupling component of general formula (Kawa) to obtain an azo dye of general formula (1).

Alternatively, instead of the compound of general formula (V),
A 7'zo dye of the general formula (IJ) can also be obtained by using the β-hydroxyethyl sulfone compound represented by (), reacting in the same manner as above, and finally esterifying with a sulfating agent.

In the above production method, any of the diazotization and coupling reactions can be carried out according to conventional methods, and the condensation reaction can also be easily carried out according to the well-known method of dehydrogenation condensation 8.

In the azo dye thus obtained, the sulfatoethylnulfonyl group can be easily changed by the action of an alkali to form an azo dye having a hinylnurponyl group.

The dyes obtained by the process of the invention can be applied to a wide range of substances having hydroxyl or amino groups, in particular textile materials, such as wool, silk, synthetic polyamides and natural or recycled celluloses, such as cotton or viscose rayon materials, by water-soluble reaction. It can be dyed according to the usual methods carried out with dyes.

For example, in the case of cellulosic 4am, dyeing is carried out using the dye according to the invention and an acid binder, such as caustic soda, sodium carbonate, phosphate, silicate or sodium bicarbonate. The dyeing method can be selected depending on the properties and physical shape of the fiber, such as exhaustion method, textile printing method, cold pad batch-up method, etc. In the case of exhaustion method, sodium carbonate, triphosphoric acid sodium,
It is carried out at relatively low temperatures in a dye bath containing mirabilite or common salt in the presence of an acid binder such as caustic soda. In the case of printing processes, pastes such as, for example, sodium alginate or starch ethers or emulsifying pastes, and sodium carbonate, sodium bicarbonate, caustic sorter, sodium triphosphate, sodium trichloroacetate or corresponding potassium or alkaline earth compounds are used. applied to the fibers together with alkaline or alkali-releasing agents, optionally with the addition of customary printing aids or dispersants, such as urea, dried and heat treated, especially in the presence of water vapor. It can be dyed by applying it to. In the case of cold-pad-bunch-up dyeing, caustic sorter alone or in combination with sodium silicate, sodium carbonate, or trisodium phosphate may be used as the acid binder, optionally with the addition of glauber's salt or common salt. In some cases, it can be dyed by padding it onto a fiber at room temperature with the addition of a solubilizing agent or penetrating agent such as urea, winding it up into a roll, leaving it for 8 hours or overnight, washing with water, and drying.

The dyed cellulose fiber thus obtained has good oil fastness, sunlight fastness, and chlorine fastness, and also has good discharge printability. The dyes according to the invention also have high fiber reactivity, good fixing properties and give dyeings of significantly high color strength at relatively low temperatures.

The present invention will be explained by examples.

In the text, parts indicate parts by weight.

Example 1 Add 25.2 parts of 2-amino-I-sulfo-5-amine methylnaphthalene to 400 parts of ice water, add 21 parts by volume of concentrated hydrochloric acid, and then dropwise add 21 parts by volume of 85% sodium nitrite solution. .

At the end of the dropwise addition, the diazotizing acid precipitates.

On the other hand, l-hydroxy-8-acetylamino-8,6-
86.1 parts of thissulfonaphthaleno was dissolved in 800 parts of water,
The solution is cooled by the addition of ice and 28 parts of sodium bicarbonate are added. This suspension is added to the diazotization solution to perform a coupling reaction.

After the coupling is completed, the precipitated dye is separated from P and soaked in ice water for 10 minutes.
Add to 0 volumes and adjust the pH to 6. 18.4 parts of cyanuric chloride is added to this solution at 0° C., and the pH is kept constant by adding 2N caustic soda solution. After the reaction was completed, a solution consisting of 1 oz of water and 28 N of 1-aminobenzene-8-β-sulfatoethyl sulfone was added to adjust the pH.
5±0.5 and raise the temperature to 30-85°C. After the reaction was completed, sodium chloride was added to precipitate crystals, followed by suction filtration to separate the dye. After separation, a powder was obtained which dissolved in water and gave a clear red color. This dye has the following structure as the free acid.

5O2CH2CH20SO3H [Dyeing example] 200 parts of the dye produced according to Example 1 + 110.8 parts
Dissolves in water of s. After adding 10 parts of cotton to this, the temperature was raised to 60°C over 10 minutes, and then 20 parts of anhydrous sodium sulfate was added.
and staining was continued for 80 minutes. Next, 4 parts of anhydrous sodium carbonate was added to this, and staining was carried out at 60° C. for 60 minutes. Next, wash with water and soap. A bright red dyeing is obtained which has outstanding stability against moisture, sunlight and the effects of chlorine.

Further, a similar dyed product can be obtained by dyeing in the same manner as above using an azo dye represented by formula (1) in which the sulfatoethylsulfonyl group is a hinylsulfonyl group.

In the table below, an equivalent amount of the azo component in column 1 is used in place of ■-hydroxy-8-ayatheramino-3,6-disulfonaphthalene, and in place of l-amino-8-β-sulfatoethyl sulfate In the second column, aminoaryl-β
By following the procedure of Example 1 but using an equivalent amount of -sulfatoethylsulfone, useful dyes having the hues indicated in the right column were obtained.

Table-1 Example 2 2-amino-l-sulfo-5-aminonaphthalene 25.
2 parts are dissolved in 800 parts of water at pH 6. 18.4 parts of cyanuric chloride are added at 0°C and the pH is kept constant by adding 2N caustic soda solution. After the reaction is complete, a solution of 7 parts of thorium nitrite in 50 parts of water is added and poured into 25 parts of concentrated hydrochloric acid and 100 parts of crushed ice.

After 1 hour, excess nitrous acid is decomposed and removed with sulfamic acid. To the diazo solution thus obtained, l -(8'-sulfophenyl)-8-methylhyrazolone-+5+ 25
．． 4 parts and adjust the pH to 5.5 with 2N caustic soda solution. ±1
Adjust to. After the coupling is completed, add 100 parts of water and l-
A solution consisting of 28 m of aminobenzene-8-β-sulfatoethyl sulfone is added. Adjust the pH to 5±05 and raise the temperature to 30-85°C. After the reaction is completed, 70 parts of sodium chloride is added to precipitate crystals, which are filtered with suction, washed, and dried at 60°C. A dye that dissolves in water turns yellow. This dye emits the following composition structure as a free acid.

[Dyeing example 5O3H 0.8 part of the above dye (I3) was dissolved in 200 parts of water,
Add 20 parts of Glauber's salt, add 10 parts of cotton, raise the temperature to 50°C, and after 20 minutes, add 4 parts of soda carbonate. Dye for 1 hour at that temperature. After dyeing, washing and soaping were performed to obtain a yellow dyed product with good durability.

Similarly, 1-aminobenzene-3-β-/2.
7L/ 7-Artethylsulfone is replaced by ■ in Table-2.
The compounds in the column are 1-(8'-sulfophenyl)-8-
Use of the azo component in column 2 of Table 2 in place of methylpyrazolone-(5) also yields useful dyes that give the hues shown in the right column.

Table 2 Example 3 25.2 parts of 2-amino-1-sulfo-5-aminomethylnaphthalene is dissolved in 800 parts of water at pH 6. 18.4 parts of cyanuric chloride are added at 0.degree. C. and the pH is kept constant by adding 2N caustic soda solution. After the reaction was completed, io parts of water and 28 parts of 1-aminebenzene-3-β-sulfatoethyl sulfone were added, and the pH was adjusted to 5±0.
5 and raise the temperature to 80-85°C. After the reaction is complete, add a solution consisting of 7 parts of nitrous acid and 50 parts of water, and pour into 25 parts of concentrated hydrochloric acid and 100 parts of crushed ice. After 1 hour, excess nitrous acid is decomposed with sulfamino acid. Remove. 200 parts of water and 1,4-dimethyl-8-sulfo-6
- A solution consisting of 21 parts of hytroquine pyridol 2-one is poured into the diazo solution. Add sodium carbonate solution dropwise to adjust pH
Adjust the value to 3.5. After the coupling was completed, sodium chloride was added to precipitate crystals, followed by suction filtration to separate the dye. This dye has the following structure in free acid form.

When this dye is dyed in the same manner as in the dyeing example of Example 1, a bright greenish yellow dyeing with wet and sunlight fastness is obtained.

Similarly, 1,4-dimethyl-3-sulfo-6- of Example 3
1 in Table 3 instead of human troquimpi rid-2-one
Useful dyes that give the hues shown in the right column can also be obtained by using the compound in column (2) in place of 1-aminobenzene-3-β-sulfatoethylnurphone for components A and Z in column A and Z in the column.

Claims (1)

[Scope of Claims] An aminonaphthalene compound represented by the following general formula (It) 03H (wherein R represents a hydrogen atom or a lower alkyl group) is diazotized and combined with the general formula (III) H-D ( III) (In the formula, D represents a residue of the coupling component.) The following general formula (IV) obtained by coupling the coupling component represented by HNCH2 (wherein, D and R have the above meanings) Azo compounds represented by 7) and anilines represented by the following general formula (V) or (■) (wherein, Xl and X2 represent a hydrogen atom, a methyl group, a methoxy group, or a sulfonic acid group) The compound is condensed with cyanuric chloride in any order, and when the aniline compound represented by the general formula (Vl) is used, it is then sulfuric esterified, or the aminonaphthalene compound represented by the general formula (old), and the general formula (V)
Or the following general formula (■) obtained by condensing the aniline compound represented by (Vl) with cyanuric chloride in any order: 0sH (wherein, Y represents a hydrogen atom or a sulfo group, R,
1+X2 has the meaning given above. ) is diazotized and coupled with a coupling component represented by general formula (III), and when an aniline compound represented by general formula (Vl) is used, it is then sulfuric esterified. A method for producing an azo dye represented by the following general formula (wherein D , + R+ Xi + X2 have the above-mentioned meanings) in the form of a free acid.