JPS594653A - Novel monoazo compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [D is phenyl which is replaced with 1-3 substituent groups selected from the groups consisting of methyl, ethoxy, halogen, acetylamino, nitro, sulfonic group, etc., or naphthyl which is replaced with 1-3 sulfonic groups; X is -(thio)sulfate ethyl, vinyl, etc.; Y is H, chlorine, or sulfonic group; Z is H, or methyl; R is 1-4C alkyl] in the form of a free acid. EXAMPLE:A compound shown by the formula II. USE:For dyeing or printing fibers such as cellulose, polyamide, polyurethane, etc. and leather in orange-based color. PROCESS:An amine shown by the formula D-NH2 is diazotized, coupled with N-acylated 7-amino-4-hydroxynaphthalene-2-sulfonic acid, etc., and hydrolyzed, to give a monoazo compound shown by the formula III. This compound is primarily condensed with cyanuric chloride to give a dichlorotriazinyl compound, which is secondarily condensed with a compound shown by the formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to fiber-reactive compounds useful for dyeing and printing cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers or leather.

More specifically, the present invention provides compounds of the following general formula (I) in the form of free acids (wherein D is a methyl group, an ethyl group, a methoxy group, an ethoxy group, a halogen, an acetylamino group, a propionylamino group, a benzoylamino group, a phenyl group substituted with 1, 2 or 3 substituents from the group consisting of a succinylamino group, a maleylamino group, a nitro group, a sulfonic acid group and a carboxyl group, or with 1, 2 or 8 sulfonic acid groups; Represents a substituted naphthyl group. X is β-sulfatoethyl, β-thiosulfatoethyl, β-
It represents ethyl phosphate, β-chloroethyl or vinyl, Y represents a hydrogen atom, a chlorine atom or a sulfonic acid group, and 2 represents a hydrogen atom or a methyl group. R is carbon number 4
Represents a low alkyl group up to. ) relates to a bifunctional fiber-reactive compound represented by

The compounds of the invention exist in the form of free acids or in the form of their salts,
Particularly preferred are alkali metal salts and alkaline earth metal salts, especially sodium salts, potassium salts, and calcium salts.

When the compounds of the invention are used for dyeing and printing textile materials, alkali metal salts are particularly preferred.

The compound of the present invention can be produced, for example, in the following manner.

An aromatic amine represented by the following general formula (ShunD-NH2(TI) (in the formula has the above meaning) is diazotized in an aqueous medium by a conventional method to obtain 7-amino-4-hydroxynaphthalene- 2-Sulfonic acid N-
A coupling reaction was performed with an acylated product or an N-methyl-N-acylated product at a temperature of 0°C to 80°C without adjusting the pH to 5 to 9. The acyl group is hydrolyzed at temperature to obtain a monoazo compound of formula (I[I).

80aH"'-2 (In the formula, D and Z have the above meanings.) Then, the formula (
m) in an aqueous medium at a temperature of 0°C to 80°C.
The dichlorotriazinyl compound is obtained by primary condensation with cyanuric chloride while adjusting the pH to EI8 to pH7, followed by the general formula (TV) (wherein R, X%Y have the above-mentioned meanings). The compounds shown can be subjected to secondary condensation at a temperature of 80° C. to 60° C., with adjustment of pH 4 to pEI 7, to obtain compounds of general formula (I).

Alternatively, the compound of general formula (IV) is firstly condensed with cyanuric chloride in an aqueous medium at a temperature of 0° C. to 80° C. while adjusting the pH to pH 7.
The compound of general formula (I) can also be obtained by secondarily condensing the monoazo compound of general formula (III) at 50°C to 50°C while adjusting the pH to 4 to 7.

Alternatively, 7-amino-4-hydroxynaphthalene-2
- sulfonic acid or 7-N-methylamino-4-hydroxynaphthalene-2-sulfonic acid and a compound of formula (IV) in any order in an aqueous medium - then at a temperature of 0°C to 8°C.
While adjusting the pH to 8 to 7 at 0°C, and secondarily to 4 to 7 at a temperature of 20 to 60°C, it is condensed with cyanuric chloride to form a compound of the general formula H (wherein, 几, X, Y, Z has the above-mentioned meaning.) A monochlorotriazinyl compound represented by is obtained, and then the pEI is adjusted to a pH of 5 to 9 with a diazonium salt of an aromatic amine represented by the general formula (9) at a temperature of 0°C to 80°C. The general formula (
A compound of I) can be obtained.

The compound represented by the general formula (IV) is the following general formula (VI
) (In the formula, X and Y have the above-mentioned meanings.) Alkyl chloride, alkyl bromide, alkyl iodide, dialkyl sulfate, p-)alkyl luenesulfonate, etc. having the corresponding number of carbon atoms Depending on the alkylating agent, the temperature 20
It can be obtained by alkylation at a temperature of .degree. C. to 80.degree. C. while adjusting PEI to pH 4 to 7.

Examples of aromatic amines represented by general formula (6) include 2-aminebenzenesulfonic acid, 2-amino-5-methylbenzenesulfonic acid, 2-amino-5-ethylbenzenesulfonic acid, and 2-amino-5-methoxybenzenesulfone. Acid 2-amino-5-ethoxybenzenesulfonic acid 2-amino-5-chlorobenzenesulfonic acid 2-amino-5-bromobenzenesulfonic acid 2-amino-5-ayathylaminobenzenesulfonic acid 2-amino-5-propionylamino Benzenesulfonic acid 2-amino-5-benzoylaminobenzenesulfonic acid 2-amino-5-succinylaminobenzenesulfonic acid 2-amino-5-maleynylaminobenzenesulfonic acid 2-amino-5-nitropennesulfonic acid 2-amino -4-chloro-5-methylbenzenesulfonic acid 2-amino-5-chloro-4-methylbenzenesulfonic acid 2-amino-4-methoxybenzenesulfonic acid 2-amino-4-ethoxybenzenesulfonic acid 2-amino-4 −
Ayacylaminobenzenesulfonic acid 2-amino-4-propionylaminobenzenesulfonic acid 2-amino-4-benzoylaminobenzenesulfonic acid 2-amino-4-succinylaminobenzenesulfonic acid 2-amino-4-maleynylaminobenzenesulfone Acid 8-Amino-4-methylbenzenesulfonic acid 8-Amino-4-ethylbenzenesulfonic acid 8-Amino-4-methoxybenzenesulfonic acid 8-Amino-4-ethoxybenzenesulfonic acid 8-Amino-4-chlorobenzenesulfonic acid 8 -Amino-4-bromopennesulfonic acid 4-amino-8-methylpentene, 4-amino-8 sulfonic acid
-Ethylbenzenesulfonic acid 4-amino-8-methoxybenzenesulfonic acid 4-amino-8-ethoxybenzenesulfonic acid 4-amino-8-chlorobenzenesulfonic acid 4-amino-8-nitrobenzenesulfonic acid 2-aminobenzene-1,4 -2-aminobenzene disulfonic acid-
1,5-disulfonic acid 2-aminobenzoic acid 2-amino-4-methoxybenzoic acid 2-amino-5-methoxybenzoic acid 2-amino-4-acetylaminobenzoic acid M2-amino-
5-Athylaminobenzoic acid 2-amino-4-sulfobenzoic acid 2-amino-5-sulfobenzoic acid 4-amino-2,5-dimethylbenzenesulfonic acid 4-amino-2,5-diethylbenzenesulfonic acid 4- Amino-2,5-dimethoxybenzenesulfonic acid 4-Amino-2,5-jethoxybenzenesulfonic acid 4-Amino-2,5-dichlorobenzenesulfonic acid 4-Amino-2,5-dibromobenzenesulfonic acid 4- Amino-2-methyl-5-methoxybenzenesulfonic acid 4-amino-2-methyl-5-ethoxybenzenesulfonic acid 2-amino-5-methylbenzene-1,4-disulfonic acid 2-amino-5-ethylbenzene-1 ,4-disulfonic acid 2-amino-5-methoxybenzene-1,4-disulfonic acid 2-amino-5-ethoxybenzene-1,4-disulfonic acid 2-amino-5-acetyl abutinobenzene-1,4- 2-amino-5-propionylaminobenzene-1,4 disulfonic acid
-2-aminonaphthalene disulfonic acid-2-aminonaphthalene 1-sulfonic acid-1,5-2-aminonaphthalene disulfonic acid-
1,7-disulfonic acid 2-aminonaphthalene-1,5,
Examples include 7-1-disulfonic acid 2-aminonaphthalene-8,6-disulfonic acid 2-aminonaphthalene-8,8-disulfonic acid 2-: aminonaphthalene-8,6,8-trisulfonic acid.

The novel compounds according to the invention have fiber reactivity and can be applied to materials consisting of cellulose fibers, natural or synthetic polyamide fibers,
It has very good properties for dyeing and printing polyurethane fibers and leather.

Preferred examples of cellulose a fiber include cotton and regenerated cellulose, but also include other vegetable fibers such as linen, hemp, and jute. Polyamide fibers include natural and synthetic fibers such as wool and other animal hairs, silk, polyamide-6,
Examples include polyamide-6, polyamide-6, polyamide-11, and polyamide-4.

The compounds of the invention are particularly useful for the dyeing and printing of cellulose fibers, and the dyeing and printing are carried out by the usual methods employed for conventional reactive dyes.

That is, in the case of exhaustion method, soda carbonate, tribasic sodium phosphate,
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. It is also possible to dye using the textile printing method.For example, acid binders such as bicarbonate of soda, sodium carbonate, tribasic sodium phosphate, and caustic soda, urea, and sizing agents are used.11. << is carried out by printing a color paste containing sodium alginate or the like on the fibers, and after intermediate drying, steaming or dry heating at 10° to 200'C.

Furthermore, the dyeing according to the invention may be carried out by a continuous method or cold pad patch dyeing is also possible.

The novel compound according to the present invention exhibits excellent physical and chemical stability in dyeing stock liquids and printing paste liquids and in the presence of alkali, and has very good compatibility and excellent compatibility in ordinary dyeing and printing. It has excellent build-up properties. In exhaust dyeing, dyed products with excellent level dyeing properties are obtained with good reproducibility, relatively being influenced by bath ratio, dyeing temperature, etc.

The dyed or printed products obtained using the compounds of the present invention have high tinting strength and excellent luster and gold strength, and are excellent in various fastnesses, particularly in chlorine fastness, light fastness, and sweat/sunlight fastness.

! JP-A-57-42986 describes a dye using a compound of general formula (VI) as a condensation component of triazine, but when the compound of the present invention is used as a dyeing and printing base for fiber materials, Compared to those dyes, it has good alkali stability and shows a high exhaustion rate and fixation rate in exhaust dyeing, and also shows a high fixation rate in textile printing, so it is possible to obtain dyed products with high density. At the same time, it has excellent wash-off properties, and has the great advantage of being able to easily remove unfixed dye.

Next, the present invention will be explained by examples. In the text, the part is heavy [
Show part.

Example 1 2-(β-sulfatoethylsulfonyl)aniline 2
0 parts dissolved in 200 parts of water at pH 5, add 45 to 50 parts.
When 46 parts of diethyl sulfate was added at ℃ and stirred at the same temperature for 10 hours while adjusting the pH to 5 to 6 with a 20% aqueous sodium carbonate solution, 65% of 2-(β-sulfatoethylsulfonyl)-N-ethylaniline was obtained. obtained with a yield of .

After cooling this aqueous solution to 20-25°C, 12 parts of cyanuric chloride was added, and a 20% aqueous sodium carbonate solution was added to pH 5-5.
Stir for 5 hours while adjusting the temperature to 6. Next, 29 parts of 7-amino-4-hydroxy-8-(4-methoxy-2-sulfophenylaso)naphthalene-2-sulfonic acid was added to 8 parts of water.
A solution dissolved at pH 7 is added to 00 parts, heated to 85-40°C, and stirred at the same temperature for 5 hours while adjusting the pH to 5-6. Next, 100 parts of sodium chloride was added to precipitate crystals, filtered under suction, washed, and dried at 60°C to obtain a compound of the following formula (1).

Reference Example 1 0.8 parts of the compound represented by formula (1) is dissolved in 200 parts of water, 20 parts of Glauber's salt is added, 10 parts of cotton are added, and the temperature is raised to 60°C. Then, after 80 minutes had elapsed, 4 parts of soda carbonate was added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping showed excellent fastness. A deep scarlet dyeing was obtained.

Compounds with the structures shown in the following table were synthesized in the same manner as in Example 1,
When this was used to dye cotton according to the method of Reference Example 1, a dyed product having similar properties and the hues shown in the table was obtained.

Example 8 2-(β-sulfatoethylsulfonyl)aniline 2
0 parts dissolved in 200 parts of water at pfL 5, 80~
Add 38 parts of dimethyl sulfate at 35°C, adjust the pEI to 5 to 6 with a 20% aqueous sodium carbonate solution, and then add 38 parts of dimethyl sulfate at the same temperature.
After stirring for 0 hours, 2-(β-sulfatoethylsulfonyl)-N-methylaniline is obtained with a yield of 54%. After cooling this aqueous solution to 2() to 25°C, 10 parts of cyanuric chloride was added, and the mixture was diluted with 20% sodium carbonate aqueous solution.
Stir for 4 hours while adjusting to H5-6. Then, 7-
Amino-4-hydroxynaphthalene-2-sulfonic acid 1
A solution prepared by dissolving 3 parts in 100 parts of water to a pLI of 7 is added, and the mixture is stirred for 5 hours while adjusting the pH to 5 to 6 at 80 to 85°C. Then, after cooling to 0 to 5°C, adjust the temperature to 116 to 7 with a 2o96 sodium carbonate aqueous solution. 2-
The diazonium salt of 1.5 amino acids and 16 parts of naphthalenedisulfonic acid is added over a period of 1 hour.

After stirring at the same temperature for 8 hours, 80 parts of sodium chloride was added to precipitate crystals, filtered under suction, washed, and then heated to 60°C.
was dried to obtain a compound of the following formula (2).

(Max 4841m) Reference Example 2 0.8 parts of the compound represented by formula (2) is dissolved in 800 parts of water, 30 parts of Glauber's salt are added, 10 parts of cotton are added, and the temperature is raised to 70°C. Then, after 20 minutes had passed, 5 parts of soda carbonate was added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were performed to obtain a dyed product with a high concentration of orange color and excellent fastness.

Compounds with the structures shown in the following table were synthesized in the same manner as in Example 8,
When this was used to dye cotton according to the method of Reference Example 2, a dyed product with similar properties and the hues shown in the table was obtained.

Claims (1)

[Scope of Claims] In the form of a free acid, the following general formula or a sulfonic acid group substituted with 1, 2 or 8 substituents from the group consisting of a maleinylamino group, a 21-mouth group, a sulfonic acid group and a carboxyl group.
Represents a naphthyl group substituted with 2 or 8 atoms. X represents β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-chloroethyl, or vinyl, Y represents a hydrogen atom, a chlorine atom, or a sulfonic acid group, and 2 represents hydrogen. The atomic word represents a methyl group. 8 represents a lower alkyl group having up to 4 carbon atoms. ) A monoazo compound represented by