CS197331B2 - Process for preparing azodyes reactive with fibers - Google Patents

Abstract

A reactive dye is of the formula <IMAGE> wherein X is hydrogen, halogen, sulfo, carboxyl, sulfo-methyl, cyano or carbamoyl, each of R1 and R2 independently is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl, and Z is a sulfonaphthylamino group, and the benzene radical can contain further substituents.

Description

The invention relates to a process for the preparation of fiber-reactive azo dyes of the general formula I,

where it means

X is H, halogen, sulfo, carboxy, sulfomethyl, cyano or carbamoyl,

R 1 and R 2 independently of one another are hydrogen, C 1 -C 4 alkyl or phenyl;

The sulfonaphthylamino group and the benzene moiety optionally have further substituents. ·. .

The substituent X for halogen represents a fluorine, chlorine or bromine atom. For

R 1 and R 2 in the meaning of a C 1 -C 4 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.

The benzene radical of the formula I can have, in addition to the sulfo group SO3H, as further substituents, for example: C1 -C4 alkyl, such as methyl, ethyl and propyl, C1 -C4 alkoxy, such as methoxy , ethoxy, propyloxy and isopropyloxy, carboxy, halogen atoms such as fluorine, chlorine and bromine.

Suitable amino acid residues which are mentioned in the description of the process for the preparation of the fiber-reactive azo dyes of the formula I are possible starting materials.

Preferred are reactive dyes of formula I wherein X is sulfomethyl, cyano or carbamoyl, R1 and R2 independently of one another are hydrogen or C1-C6alkyl, Z is monosulfonaphthylamino, disulfonaphthylamino or trisulfonaphthylamino.

An important sub-group of reactive dyes of formula (I) are reactive dyes of formula (II),

wherein R 1 is hydrogen or C 1 -C 4 alkyl.

Other valuable dyes of the above structure are the reactive dyes of formula III.

The dyes of formula (I) are fiber-reactive since they contain a fluorine atom on the symtriazine residue.

Fiber-reactive dyes are those dyes that can react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides to form a covalent chemical bond.

The process for preparing a reactive azo dye of the formula I is characterized in that it is reacted optionally by diazotization and coupling and condensation in any sequence of the 6-hydroxypyridone-2 'of the formula IV,

2,46-trifluoro-sym-triazine of formula VI

X

HIM

^R (lV>)

and amino compounds of formula VII,

H-Z wherein Z is as defined above.

In the compound of formula (V), the benzene ring may be further substituted.

Alternatively, the corresponding aminoacetylaminobenzenemmonium sulfonic acid is used in place of the diaminobenzenesulfonic acid (V) or ammonioacetylaminobenzenesulfonic acid and, after diazotation and copulation, W represents a hydrogen atom or a carbamoyl group and X, R 1 and R 2 are as defined above.

With saponification, the acyl residue is cleaved again.

In the case where, in the 6-hydroxypyridone-2-Oine of formula IV, W is a carbamoyl group and X is not a hydrogen atom, the carbamoyl residue W is cleaved in the coupling according to the invention.

In a preferred embodiment, 6-hydroxypyridin-2-one of formula IV, wherein X is a sulfomethyl group, a cyano group or a carbamoyl group, R1 and R2 independently of one another are hydrogen or C1-C4alkyl, and amino compounds of formula VII wherein Z is monosulfonaphthylamino, disulfonaphthylamino or trisulfonaphthylamino.

The valuable reactive dyes of formula (II) are prepared by coupling and condensing in any sequence the 6-hydroxypyridone-2 of formula (VIII),

wherein R 1 is hydrogen, C 1 -C 4 alkyl and W is hydrogen or carbamoyl, 1,3-diaminobenzene-4-sulfonic acid, 2,4,6-trifluoromethyl-triazine, and aminonaphthalenesulfonic acid of formula IX .

(IX)

Since the above process steps can be carried out in a different sequence, or partially also simultaneously, different process variants are possible. The starting materials used in the individual partial reactions follow from formula (I). In general, the preparation is carried out in successive steps, the sequence of reactions between the individual reactants of formulas (IV) to (VII) being freely selectable.

Important variants of the preparation process are characterized in that:

1. condense the 2,4,6-trifluoro-sym-triazine of formula VI with a diaminobenzenesulfonic acid of formula V, the primary condensation product obtained is diazotized and coupled to the 6-hydroxypyridone-2 of formula IV, and finally one fluorine atom in the symtriazine residue is replaced with an amino group by condensation with an amino compound of formula VII,

2. the diaminobenzenesulfonic acid of formula V is diazotized, optionally from a

of the corresponding aminoacetylaminobenzenesulfonic acid and coupled to the 6-hydroxypyridone-2 of formula IV (and optionally the acetyl residue is cleaved by saponification), the azo compound is condensed with 2,4,6-trifluorometri-triazine of formula VI and the obtained monocondensation product is condensed with an amino compound of formula VII,

3. condense the diaminobenzenesulfonic acid of formula V with 2,4,6-trifluorometri-triazine of formula VI, the primary condensation product is condensed with the amino compound of formula VII, the resulting secondary condensation product is diazotized and coupled to 6-hydroxy-pyridine -2 of formula IV,

4. diazotize the diaminobenzenesulfonic acid of the formula V, optionally the corresponding aminoacetylaminobenzenesulfonic acid and coupled to the 6-hydroxypyridone-2 of the formula IV (and optionally the acetyl residue is cleaved by saponification), further condensing 2,4,6-trifluoromethyl-triazine of formula VI and the amino compound of formula VII and the two intermediates condense with each other,

5. condense the 2,4,6-trifluoro-sym-triazine of formula VI with the amino compound of formula VII, the monocondensation product is condensed with the diaminobenzenesulfonic acid of formula V, the resulting secondary condensation product is diazotized and coupled to 6-hydroxypyridone- 2 of formula IV.

In the following examples, the preparation of intermediates is not always described, but follows without further comment.

The starting materials used in the process for preparing the fiber-reactive azo dyes of the formula I are:

6-hydroxypyridones-2 of formula IV:

1-ethyl-3-carbamoyl-4-methyl-6-hydroxypyridone-2,1,4-dimethyl-3-carbamoyl-6-yl-TOxypyridone-2,1-ethyl-3-sulfomethyl-4-methyl-6- hydroxypyridone-2,1-phenyl-3-sulfo-methyl-4-methyl-6-hydroxypyridone-2,

3-sulfomethyl-4-methyl-2,6-dihydroxypyridine-2,3-cyano-4-methyl-2,6-dihydroxypyridine, 1-ethyl-3-cyano-4-methyl-6-hydroxypyridone-2,3 carbamoyl-4-methyl-2,6-dihydroxy-l-ethyl-3-sulfomethyl-4-methyl-5-carbamoyl-6-hydroxypyridone-2, ¹ 3-sulfomethyl-4-methyl-5-carbamoyl-2,6 -dihydroxypyridine, 1-ethyl-3-cyano-4-methyl-5-carbamoyl-6-hydroxy-oxypyridone-2;

diaminobenzenesulfonic acids? formula V:

1,3-diaminobenzene-4-sulfonic acid,

1,4-diaminobenzene-2-sulfonic acid, 1-amino-3-acetylaminobenzene-4-sulfonic acid (additional saponified), 1-amino-4-acetylaminobenzene-2-sulfonic acid (subsequently saponified), 1-amino-3-acetylamino -6-methylbenzene-4-sulfonic acid (saponified), 1-amino-3-acetylamino-6-methoxybenzene-4-sulfonic acid (saponified),

1,3-diaminobenzene-4,6-disulfonic acid,

1,4-diaminobenzene-2,5-disulfonic acid,

1,4-diaminobenzene-2,6-disulfonic acid;

2,4,6-trifluoro-sym-triazine of formula VI, cyanurfluoride;

amino compounds of formula VII:

1-naphthylamine-2-sulfonic acid, 1-naphthylamine-3-sulfonic acid, 1-naphthylamine-3-sulfonic acid, 1-naphthylamine-4-sulfonic acid, 1-naphthylamine-5-sulfonic acid, 1-naphthylamine -6-sulfonic acid, 1-naphthylamine-7-sulfonic acid,

1-Niaffylamine-8-sulfonic acid

2-naphthylamine-1-sulfonic acid, 2-naphthylamine-3-sulfonic acid, 2-naphthylamine-4-sulfonic acid, 2-naphthylamine-5-sulfonic acid, 2-naphthylamine-6-sulfonic acid, 2-naphthylamine- 7-sulfonic acid, 2-naphthylamine-8-sulfonic acid, 1-naphthylamine-2,4-disulfonic acid, 1-naphthylamine-2,5-disulfonic acid, 1-naphthylamine-2,7-disulfonic acid, 1-naphthyl mln-2,8-disulfonic acid, 1-naphthylamine-3,5-disulfonic acid, 1-naphthylamine-3,6-disulfonic acid, 1-naphthylamine-3,7-disulfonic acid, 1-naphthylamine- 3,8-disulfonic acid, 1-naphthylamine-4,6-disulfonic acid, 1-naphthylamine-4,7-disulfonic acid, 1-naphthylamine-4,8-disulfonic acid,

1-naphthylamine-5,3-disulfonic acid,

2-naphthylamine-1,5-disulfonic acid, 2-naphthylamine-1,6-disulfonic acid, 2-naphthylamine-1,7-disulfonic acid, 2-naphthylamine-3,6-disulfonic acid, 2-naphthylamine ^J 3, 7-disulfonic acid, 2-naphthylamine-4,7-disulfonic acid, 2-naphthylamine-4,8-disulfonic acid; 2-naphthylamine-5,7-disulfonic acid, 2-naphthylamine-6,8-disulfonic acid, 1-naphthylamine-2,4,6-trisulfonic acid, 1-naphthylamine-2,4,7-trisulfonic acid, 1- naphthylamine-2,4,8-trisulfonic acid, 1-naphthylamine-2,5,7-trisulfonic acid, 1-naphthylamine-3,5,7-trisulfonic acid, 1,1-naphthylamine-3,6,8-trisulfonic acid , 1-naphthylamine-4,6,8-trisulfonic acid,

2-naphthylamine-1,3,7-trisulfonic acid, 2-naphthylamine-1,5,7-trisulfonic acid, 2-naphthylamine-3,5,7-trisulfonic acid, 2-naphthylamine-3,6,7- risulfonic acid, 2-naphthylamine-3,6,8-trisulfonic acid, 2-naphthylamine-4,6,8-risulfonic acid.

The diazotization of the diaminobenzenesulfonic acids of formula (V) is generally carried out by treatment with nitrous acid in an aqueous solution acidified with mineral acid at low temperature by coupling to the 6-hydroxypyridone-2 of formula (IV) at a weak acidic, neutral to weak alkaline pH.

The condensation of 2,4, (.beta.-trifluoromethyl-1-iriazine) with the diaminobenzenesulfonic acids of the formula V and with the amino compounds of the formula VII is preferably carried out in an aqueous solution or in an aqueous suspension at low temperatures. and at a weak acid, neutral or weak alkaline pH, preferably the hydrogen fluoride which is released during condensation is continuously neutralized by the addition of aqueous alkali hydroxides, carbonates and acidic carbonates.

The fiber-reactive azo dyes of the general formula I prepared by the process according to the invention are characterized by a high reactivity and a high degree of fixation.

They are suitable for the dyeing and printing of a wide variety of textile materials such as silk, - leather, wool, polyamide fibers, polyurethane fibers, but especially for the dyeing and printing of cellulosic fibrous web materials such as flax, cellulose staple, regenerated cellulose and in particular cotton.

It is suitable for both pull-out dyeing and flaring dyeing, wherein the textile material is impregnated with an aqueous and optionally salt-containing dye solution and the dye is fixed after alkaline treatment - or in the presence of an alkali - optionally under heat.

It is also suitable for printing on a particular cotton, but also for printing on nitrogen-containing fibers, such as wool, silk or wool blend.

It is recommended that the dyeings and prints be thoroughly rinsed with cold and - then hot water, possibly with additives - dispersant and diffusion enhancers ¹ .

In the following examples, parts are by weight and temperatures are given as - - ° C.

Example 1

39.5 parts of ethyl 4-methyl-5t (5'-amino-2'-sulfonylenedio) -6-oxy-2-pyridone-3-carboxamide, obtained by coupling 3-amino-3-aminoacetate-4-sulfonic acid to 1-ethyl-4-methyl-6-oxy-2-pyrido-3-carboxamide and subsequent saponification is dissolved - in 500 parts - water with sodium hydroxide at pH -7- and cooled to 0 by addition of ice. to 5 ° C. 14 parts of cyanurofluoride are added and the pH is maintained at 8 with sodium hydroxide solution. After 20-30 minutes, a neutral solution of 22.2 parts of 2-naphthylamine-6-sulfonic acid in 150 is added. Water was added and the pH was maintained at 8 by further addition of sodium hydroxide solution while the temperature rose to 40 ° C. After about 30 minutes of stirring, 75 parts of potassium chloride precipitate, mix again, then. aspirates and. dried. Dye formulas

is a yellow powder and dyes cotton. for brilliant · slightly greenish yellow shades with very good fastness.

Colorants with the same shades and with similar stability are obtained when the following naphthylamine monosulfonic or naphthylaminedlsulfonic acids or mixtures thereof are used in place of 2-naphthylamine-6-sulfonic acid as described above:

1-naphthylamine-4-sulfonic acid, 1-naphthylamine-5-sulfonic acid, 1-naphthyl-6-sulfonic acid, 1-naphthylamine-7-sulfonic acid,

1-naphthylamine-8-sulfonic acid,

2-naphthylamine-6-sulfonic acid, 2-naphthylamine-7-sulfonic acid, 1-naphthylamine-3,6-disulfonic acid,

1-naphthylamine-,73,7-disulfonic acid,

2-n ₍ aftylamine-1,5-disulfonic, 2-naphthylamine-3,6-disulfonic, 2-naphthylamine-4,8-disulfonic, 2-naphthylamine-5,7-disulfonic, 2-naphthylamine-6,8- dlsulfonic, 1-naphthylamine-2-sulfonic,

1-naphthyl-3-sulfonic acid,

2-naphthylamine-1-sulfonic acid, 2-naphthylamine-3-sulfonic acid, 2-naphthylamine-4-sulfonic acid, 2-naphthylamine-8-sulfonic acid, 1-naphthylamine-2,7-disulfonic acid, 1-naphthylamine-3,8- disulfone,

1-naphthylamine-4,8-disulfonic acid,

2-naphthylamine-4,7-disulfonic acid, 1-naphthylamine-2,5,7-trisulfonic acid, 1-naphthylamine-2,4,8-trisulfonic acid, 1-naphthylamine-3,6,8-trisulfonic acid,

1-naphthylamine-4,6,8-trisulfonic acid,

2-naphthylamine-1,5,7-trlsulfonic acid, 2-naphthylamine-4,6,8-risulfonic acid and 2-naphthylamine-3,6,8-trisulfonic acid.

Example 1 a d 2

18.8 parts of 1,3-phenylenediamine-4-sulfonic acid are dissolved in 250 parts of water at pH 7.a at 0 DEG C. and 14 parts of cyanurfluoride are added. Stir at 0 to 5 ° C, maintaining the pH at 7 to 8 by dropping · 52 parts of 2N sodium hydroxide solution. Once more of the hydroxide solution is no longer received, 22.2 parts of 2-naphthylamine are dissolved. 6-sulfonic acids in 150 parts of water under neutral reaction and added to the reaction mixture, heated to 40 ° C and maintained at pH 7 to 8 by further addition of sodium hydroxide solution. at 0 ° C. Acidify with 25 parts concentrated. hydrochloric acid and diazotized with 25 parts of a 4N sodium nitrite solution. It is then stirred briefly, destroying any excess nitrite and leaving; A neutral solution of 19.6 parts of ethyl 4-methyl-G-oxy-4-pyridone-5-carboxamide in 100 parts is added. water. Add sodium hydroxide solution. first adjust the pH to. After completion of the coupling, increase to 7 and the product is precipitated with 70 parts of potassium chloride.

The same dye as described was obtained. in Example 1.

Dyes of similar properties are obtained when the diamines from column II of the following table are reacted with cyanurfluoride by condensation, the condensate is reacted with the naphtha-aminosulfonic acid listed in column III and after diazotization the product is coupled to the pyridone listed in column IV the following tables. The color shade is given in column V.

TABLE 1

III

IV

IN

I II

^h '- ⁿ j' ^nw '· hos ^^ soh W-QQ-SV CW3 wo ₃ ^sec - <WS 3 3 ст ^ ^Л о ^ AND CH _{3 HOjS} ^ ‘-CQ Ο ^ ΌΗ ήΑ- · ^ ^S0 3 ^W CHpi ₃ Honor. ^ ⁼ ° ° Λ Q ^ ir ^ OH CH ₃

greenish yellow greenish yellow redish yellow

yellow greenish yellow yellow greenish yellow scp

SO.H

IV снсц

yellow yellow

V - +

greenish yellow greenish yellow greenish yellow greenish yellow greenish yellow

S / ηβ 5 ^ Sat ₃ h

S ₃ H ₃ Sa ₃ h

SO.H

_сн л сн ₃

СНЛКСН ^ greenish yellow

Example 3

If one equivalent of 2-naphthylamine-6-sulfonic acid is first condensed with 1 equivalent of cyanurofluoride and the product is then condensed with. 1 equivalent of 1,3-phenylenediamine-4-sulfonic acid and otherwise proceed as described in Example 2 to give the same dye of the same quality.

Example 4

Neutral solution of 39.5 parts of 1-ethyl-4-methyl-5- (5‘-amino-2‘-sulfophenylazo) -6-oxy: 2-pyridone-3-carboxamide in 500 parts of water at 0 ° C. at 0-5 ° C is mixed with the suspension

33.8 parts of freshly prepared 2- (2'-naphthylamino) -4,6-difluorotriazine-8'-sulfonic acid, stirred well and maintained at pH 5 by addition of 20% sodium carbonate solution while maintaining the temperature. rise to 20 [deg.] C. After completion of the condensation with a mixture of sodium chloride and potassium chloride, the dye is salted out, sucked off and dried.

^SO 3 ^H dyes cotton from a long bath to a brilliant yellow shade with a green tint, highly stable.

Dyes of similar properties can also be prepared as described in Example 4 when 2,4-difluoro-2- (naphthylamino) -1,3,5-triazine sulfonic acid in column II of the following table is reacted with the color-delivering compound shown in column III and the reactive dye thus obtained is isolated in a manner known per se. The prepared dyes dye cotton (or other fibers) to the shades shown in column IV.

TABLE 2

CH 4 H, v

C-NH ₃ s

P-NH

HO.S

strong greenish yellow

strong greenish yellow

CH.

HCLS-CH.

yellow

ch ₃

ŽlutýγΛγ NN ^NH * ho yellow

greenish yellow

Example 5

26.8 parts of 1,4-phenylenediamine-2,5-disulfonic acid are dissolved in 300 parts of pH 7 water at 0 ° C. With vigorous stirring and caustic addition, 14 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise while maintaining a pH of 6.5-7.5 and maintaining the temperature at 0 ° with the addition of ice. C. After 1 equivalent of sodium hydroxide solution is consumed, 22.3 parts of 2-naphthylamine-5-sulfonic acid are added, heated to 40 ° C and the pH is maintained at 8 by the addition of 1 equivalent of sodium hydroxide solution. After completion of the condensation, it is cooled to 0-5 [deg.] C. by addition of ice, acidified with 30 parts of concentrated hydrochloric acid and diazotized by dropwise addition of 7 parts of sodium nitrite dissolved in water. The diazo compound suspension is allowed to flow into a suspension of 19.6 parts of 1-ethyl-6-hydroxy-4-methyl-2-pyridone-3-carboxamide in 300 parts of water. The pH is then adjusted to a pH of 4 and after a certain time with sodium hydroxide solution. mixing time to 7. Finished dye formula

The precipitate was collected by sodium chloride and collected. The yellow powder obtained dyes cotton to very stable yellow shades.

However, if the same procedure is followed but using the diamines, naphthylamine sulfonic acids and the coupling components listed in Table 3, in the appropriate sequence and in appropriate amounts, additional dyes are obtained which dye the cotton to the shades shown in Table 3.

TABLE 3

сн _А сн ₄ сн _л си ₃ ch

НО'УГЪн

ό'ΊΑΟΗ

СН (СН ₃ ) ^

НО ^ СН ^ А thiXrOH

AND

CH (CH ₃ ) _Z greenish yellow yellow greenish yellow yellow

SO.H i

SO.H

CH ^{Ho s'} CH _{R f} and _y co-Nw _L

HO ₃ S-CH он

yellow yellow yellow yellow

4 5 Q greenish I-CQ I * yellow o γ он сн ^ сн, ^CH 3 yellow O ^ N ^ OH CH ₃ HOOC ^ K ο> Λομ ^С Щ yellow CH, “Λ o γ ^ ο μ yellow ^c Vh ₃

1β

Example 6

To an ice-cold, neutral solution of 4.46 parts. 2-naphthylamine-1-sulfonic acid. in 75 parts water, a solution of 2.97 parts cyanurfluoride in 5 parts toluene was added dropwise over 10 minutes with good stirring. The pH of the mixture is maintained at 6 to 7 with sodium hydroxide solution. After acylation, the suspension is poured into a neutral solution of 7.90 parts of 1-ethyl-4-methyl-5- (5'-amino-2'-sulfophenylazo). 6-oxy-2-pyridone-3-carboxamide and the mixture is heated to 30-35. ° C, while maintaining the pH by further adding IN solution. of sodium hydroxide to 7-8. Potassium chloride will salt the resulting reactive dye of the formula

filtered, mixed with a concentrated aqueous solution of 1 part dinatrium hydrogen phosphate and dried in vacuo. The dye dyes cotton to pure greenish yellow shades.

Acylation in paragraph 2 of the following table of said pyridone azo dye with difluorotriazine derivatives of the naphthylamine sulfonic acids listed in column 3 provides additional dyes which:. color cotton. to shades in column .4.

TABLE 4

2-Aminonaphthalene-3,6-disulfonic acid

- aminonaphthalene-3,6-disulfonic acid greenish yellow yellow

2-Aminonaphthalene-4,8-disulfonic acid yellow

2-Aminonaphthalene-4,8-disulfonic acid

2-Aminonaphthalene-4,8-disulfonic acid

1-naphthylamine-2-sulfonic acid

2-aminonaphthalene-1,5-disulfonic acid

1-aminonaphthalene-2,7-disulfonic acid yellow greenish yellow greenish yellow greenish yellow greenish yellow

1-Aminonattalene-2,7-disulfonic acid yellow

CHiCHi 1-aminonaphthalene-2,7-disulfonic acid 1-aminonaphthalene-2,7-disulfonic acid • 2-naphthylamine-3,6,8-trisulfonic acid

CU ₂ CH ₃ 1-naphthylamine-8-sulfonic acid

1-naphthylamine-2,7-disulonic acid

-Z ' ³ ™ ³

2-naphthylamine-3,6-disulonic acid yellow yellow greenish yellow greenish yellow greenish yellow 'greenish yellow

2-naphthylamine-3,6-disulonic acid greenish yellow

Example 7

Ice cold, neutral solution 51 parts 2,4-difluoro-6-3'- [1'-ethyl-3'-carboxyimido-4'-methyl-6'-hydroxy-2'-pyridone-5'-azo] Anilino-1,3,5-triazine-4'-sulfonic acid in 600 parts of water is mixed with a neutral solution of 22.4 parts of 2-naphthylamine-5-sulfonic acid in 100 parts of water. While stirring well, the temperature is allowed to rise slowly to 70 ° C while maintaining the pH at 7 by dropwise addition of 2N sodium hydroxide solution. Upon complete condensation, the dye of the formula precipitates with sodium chloride

it is not treated with a solution of 5 parts dinatrlumhydrogen phosphate in water and dried. The dye dyes cotton from a long bath to permanent greenish yellow shades.

Similar dyes can be produced if the difluorotriazine listed in column 2 of the following table is reacted with the naphthylamine sulfonic acid equivalent of column 3 in the same manner as described above. The reactive dye thus obtained dyes cotton to the shade shown in column 4, the dyeing being very stable.

TABLE 5

H 0 ₃ $ Ц

HO ^ CH,

HO ₃ S * CW

НО / -СЦ

HjN-CO

снсн strong greenish yellow strong greenish yellow strong greenish yellow strong greenish yellow strong greenish yellow strong greenish yellow greenish yellow o γ он но 'сн _А сн, o

- _p

............. Ch o ^^ hqX CH ^ CH3Cj

O ch

H OjSOH ^^ sj ^^ jp. h · = h— о П он hco> v & CfWh

CH ₃ CH ₃

CH

HjH-CO-H ^with N

C)

CH ₂ CH ₃ greenish yellow

yellowish yellowish greenish yellow

WOjS СЦСН ^ СН

Ν ~ Ν ·

MO.S

О ^ СН ^ И,

CH ^CW ». ^C W ^W 3 green-yellow

Dye prescription

Dyeing Procedure II parts of the dye prepared as described in Example 1 were dissolved with the addition of 0.5 parts of m-nitrobenzenesulfonic acid sodium salt in 100 parts of water. The resulting solution is soaked in a cotton fabric so that it receives 75 weight and dried.

The fabric is then impregnated with a 20 ° C solution containing 5 g of sodium hydroxide and 300 g of sodium chloride per liter, squeezed to a weight of 75 Why, steaming for 30 seconds at 100 to 101 ° C, rinsing Wash and soap for a quarter of an hour in a 0.3% boiling solution of nonionic detergent, rinse and dry.

parts of the dye prepared as described in Example 1 are dissolved in 100 parts of water.

The solution is added to 1900 parts of cold water, 60 parts of sodium chloride are added and 100 parts of cotton fabric are placed in the dye bath.

The temperature is raised to 40 ° C, after 30 minutes add 40 parts of soda ash and again 60 parts of sodium chloride. The temperature is maintained at 40 ° C for 30 minutes, rinsed, and the dyeing is then soaped for 15 minutes with a 0.3% boiling solution of nonionic detergent, rinsed and dried.

Claims (4)

CLAIMS 1. A process for the preparation of a fiber-reactive azo dyes of the general formula I, in which: X is hydrogen, halogen, sulfo, carboxy, sulfomethyl, cyano or carbamoyl, R 1 and R 2 independently of one another are hydrogen, C 1 -C 4 alkyl or phenyl; The sulfonaphthylamino group and the benzene radical optionally have further substituents, characterized in that they are reacted, optionally by diazotization and coupling and condensation in any sequence, of the 6-hydroxypyridone-2 of the formula IV, X HO г -Ч / Ло (IV) wherein W represents a hydrogen atom or a carbamoyl group and X, R 1 and R 2 are as defined above, a diaminobenzenesulfonic acid of formula V, 2. A process according to claim 1, wherein the starting material is 6-hydroxypyridon-2-one of formula IV, wherein X is a sulfomethyl group, a cyano group or a carbamoyl group, R1 and R2 are each independently hydrogen or alkyl. C 1 -C 4, and amino compounds. of formula VII, wherein Z is monosulfonaphthylamino, disulfonaphthylamino or trisulfonaphthylamino. 2,4,6-trifluoro-sym-triazine of formula VI C-F I P N p (V 1) and amino compounds of formula VII, H — Z,. wherein Z is as defined above. 3. The method of item 2 for preparing a fiber-reactive azo dye of the general formula II, (Π) wherein R1 is hydrogen or. (C 1 -C 4) -alkyl, characterized in that: 6-hydroxypyrido-n-2 of the general formula VIII, wherein R 1 is hydrogen or C 1 -C 4 alkyl and W is hydrogen or carbamoyl, 1,3-diaminobenzene-4-sulfonic acid, couples and condenses in any sequence ,. 2,4,6-trifluoromethyltriazine and aminonaphthalenesulfonic acid of formula IX. I / X) J 4. The method of item 3 for preparing a fiber-reactive azo dyes of the formula III, HJ1-CO characterized by diazotizing 1-amino-3-acetylamino-6-sulfonic acid and coupling to 1-ethyl-4-methyl-5-carbamoyl-6-hydroxypyridone- (2), the acetyl group is cleaved by saponification , the ammonium compound obtained is condensed with cyanurfluoride and the primary condensation product obtained is condensed with 2-aminonaphthalene-6-sulfonic acid.