DE4203279A1 - New reactive red mono- or dis-azo dye(s) - Google Patents

Abstract

Fluoro-s-triazinyl-substd. mono- or disazo reactive dyes of formula (I) (in free acid form) are new: K = aniline residue of formula (i) or aminonaphthol-sulphonic acid residue of formula (ii), when K is bonded to the triazine ring via the amino function; x, y = 0 or 1; Y = CH=CH2, CH2CH2OSO3H or CH2CH2Cl; R = H or 1-3C alkyl (opt. substd. by OH, COOH or CN); Z = H, 1-4C alkyl or 1-4C alkoxy; D = (a) phenyl or naphthyl, both substd. by SO3H, COOH, CH2SO2W, SO2W, NHCOMe, 1-4C alkyl and/or 1-4C alkoxy; or (b) an azobenzene residue of formula (iii): W = as defined for Y; Q = H or Me; z = 1 or 2; A = H, 1-4C alkyl or 1-4C alkoxy; B = H, 1-4C alkyl (opt. substd. by OH, SO3H or OSO3H), halogen, 1-4C alkoxy, NHCONH2, 2-5C alkanoylamino, NHCOCH2OSO3H, NHCO(CH2)z'SO3H, NHCOCH2OH or 2-5C alkoxycarbonylamino; z' = 1-3.

Description

The invention relates to novel azoreactive dyes with a monofluorotriazinyl and vinylsulfonyl reactive radical. Although combinations of reactive components are known from EP-A-94 055, EP-A-85 025, EP-A-65732, US-A-4700 038 and EP-A-3 07 817 however, this prior art has been known still application problems.

The present invention relates to mono- and disazo reactive dyes which are used as the free acid of the formula (1) correspond

in which mean
m, n are independently 0 or 1,
Y is CH = CH₂, CH₂CH₂OSO₃H or CH₂CH₂Cl,
R is H or C₁-C₃alkyl which may be substituted by OH, CO₂H or CN, in particular CH₃, C₂H₅, C₃H₇, CH₂CH₂OH, CH₂CH₂CO₂H, CH₂CO₂H or CH₂CH₂CN,
ZH, C₁-C₄-alkyl or C₁-C₄-alkoxy, in particular CH₃, C₂H₅, OCH₃, OC₂H₅ or OC₃H₇ and
D is a substituted with SO₃H, CO₂H, CH₂-SO₂W, SO₂W, NH-COCH₃, C₁-C₄-alkyl and / or C₁-C₄-alkoxy phenyl or naphthyl radical, wherein W has one of the meanings given under Y, or a rest of the structure

Dyes of the formula (2) are preferred

wherein m, R, Y and Z have the abovementioned meaning and the Phenyl or naphthyl radical D additionally by C₁-C₄- Alakyl, C₁-C₄-alkoxy, NHCOCH₃, CH₂SO₂W or SO₂W substituted can be, where W is one of the Y specified Has meanings.

Furthermore, dyes are especially preferred Formula (2) wherein D is a radical of formula (3) and (4) represents.

Particular preference is given to dyes of the formula (5a) and (5b)

wherein
V, H, CH₃, OCH₃, OC₂H₅ or NHAcyl, in particular NH-CO-CH₃,
p, m are independently 0 or 1,
RH or C₂H₅,
W, Y are independently CH = CH₂ or CH₂CH₂OSO₃H and
Z is H, CH₃ or OCH₃.

Very particular preference is given to dyes of the formula (6) and (7)

wherein p, m, R, Y and Z are those given under formula (5) Meaning.

The formulas (1) to (7) give the sulfo-containing Dyes in the form of the free acids again. In the Preparation are generally obtained the salts, in particular the alkali salts such as sodium, potassium or Lithium salts. The dyes may be in powder or as obtained and used concentrated aqueous solutions become.

The preparation of the dyes (1) takes place example, according to the following process:
Diazotization of amines D-NH₂ and coupling of the resul tierenden diazonium compounds with aminonaphthol sulfonic acid derivatives of the formulas (8).

The preparation of the intermediates (8) was carried out at For example, by amino-naphthol mono- or di sulfonic acids or (aminobenzoyl) aminonaphthol mono- or disulfonic acids on the amine function by known methods (eg EP-A-40 806, DE-A-27 11 150, EP-A-1 72 790 or US Pat DE-A-27 47 014) with trifluoro-s-triazine condensed and the resulting Difluortriazinylverbindungen with amines of formula (9)

in the presence of acid-binding agents. details to further synthesis possibilities can the following Examples are taken. Examples of the Aminonaphtholsulfonic acids are:

Suitable amines of the formula (9) are, for example:

The specified dye formulas are those of the free Acids. In the production are generally the Salts get, in particular the alkali salts like Sodium, potassium or lithium salts. The dyes can also be used as concentrated solutions become.  

The dyes can be mixed with other dyes be used for a Trichromie.

Obtained with good build-up capacity and high fixation exploit dyeings with good fastness properties, in particular Wet fastness properties.

Example 1

0.1 mol of the amino compound of the formula

are stirred in 100 ml of water and 100 g of ice and dissolved. After addition of 0.1 mol of sodium bicarbonate 0.11 mol is added dropwise at 0 ° C. within 100 minutes Trifluoro-s-triazine too. This gives about 250 ml of a aqueous solution of the condensation product of the formula

Example 1

0.1 mol of 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid are suspended in 150 ml of water and washed with a 10% solution of lithium hydroxide dissolved neutral. Adds to this one holds the above condensation solution (Example 1) and at the same time by the addition of lithium carbonate the pH between 4.0 to 4.5. After about 6 hours at 10 to 20 ° C, the secondary condensation is completed.  

0.1 mol of 2-amino-1,5-naphthalenedisulfonic acid are in diazotized known manner, and the resulting Diazonium salt mixture at pH 6.5-7.5 and 20 ° C for Solution of the coupling component added. After isolation and drying gives about 45 g of a saline red powder of the following structure

the cotton colors according to the usual dyeing and printing process for reactive dyes in red shades. (λ _max = 517, 540 nm (H₂O)).

By variation of the amine component in Example 1 as well the coupling or diazo component in Example 2 are other valuable red reactive dyes available (see Table 1).

Dye examples 2 to 48 are also accessible according to the following synthesis sequence:
First, 0.1 mol of 4-amino-5-hydroxy-2,7 (or 1,7) -naphthalenedisulfonic acid with 0.11 mol of cyanuric fluoride at 0 ° C and pH 4.0 to 4.5 in a known manner condensed Siert , And then the mono-condensation product with 0.1 mol of the amine component in increasing temperature range between 0 to 20 ° C and at pH 4.0 to 6.5 set. The pH control is carried out by means of aqueous sodium carbonate solution or potassium bicarbonate solution. In the last step of the reaction sequence are then at 10 to 20 ° C and pH 6.5 to 7.5 corresponding diazonium salts 0.1 mol) coupled to the Biskondensationsprodukt. The isolation of the dyes is then carried out as described in Example 2.

Is used in Example 2 instead of 4-amino-5 hydroxy-2,7 (or 1,7) -naphthalenedisulfonic acid ent N- (4-aminobenzoyl) derivatives are so the following red dyes are available:

Example 49

Example 50

Assuming the above variation to Example 26, so resul a likewise valuable red reactive dye.

Example 51

example 52

0.1 mol of the monoazo compound of the formula

are dissolved neutral in 500 ml of water. To this solution the ice-cold condensation solution from Example 1 is added and keeps the pH constant with 20% soda solution between 6.5 to 7.0. After about 6 hours of stirring at 10 to 25 ° C and pH 7.0 drops the dye by addition from common salt, isolated by suction and dried. This gives about 60 g of a saline red Dye powder, the formula

and the cotton in orange-red shades colors (485 nm). By variation of the amine component in Example 1 and the coupling or diazo component in Example 52 is another valuable orange and sharp Lachrote reactive dyes are available (Table 2).  

Table 2

Dye examples 52 to 93 are also accessible according to the following synthesis sequence:
First, 0.1 mol of amino-4-hydroxy-2-naphthalinsul fonsäure be reacted with the condensation solution of Example 1 at 0 ° C and pH 4.5. During the approximately 3-hour reaction time, the reaction temperature may well rise to room temperature. At pH 6.5-7.5 (sodium carbonate solution), corresponding diazonium salts (in each case 0.1 mol) are then coupled to the colorless bis-condensation products. The dyes are isolated by salting out and suctioning.

The table examples are characterized by the following λ _max values (H 2 O):

example nm 3 518, 540 4 518, 540 7 519, 540 8th 518, 540 21 521, 545 34a 521, 544 44 519, 540 53 486 54 486 56 485 66 483 66a 482 66b 483 78 502 78b 501 78c 502 79 503 80 501 82 497 86 513 87 514 88a 512

Claims (8)

1. Reactive dyes which correspond as free acid of the formula in which mean
m, n are independently 0 or 1,
Y is CH = CH₂, CH₂CH₂OSO₃H or CH₂CH₂Cl,
R is H or C₁-C₃alkyl which may be substituted by OH, CO₂H or CN,
Z is H, C₁-C₄-alkyl or C₁-C₄-alkoxy,
D is a substituted with SO₃H, CO₂H, CH₂-SO₂W, SO₂W, NH-COCH₃, C₁-C₄-alkyl and / or C₁-C₄-alkoxy phenyl or naphthyl radical, wherein W has one of the meanings given under Y, or a rest of the structure 2. Reactive dyes according to claim 1, characterized in that they correspond to the following formula wherein m, R, Y and Z have the meaning given in claim 1 and the phenyl or naphthyl radical D may additionally be substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, NHCOCH₃, CH₂SO₂W or SO₂W, where W is one of has meanings given under Y. 3. A reactive dye according to at least one of the preceding claims, characterized in that D represents a radical of the following formulas 4. A reactive dye according to at least one of the preceding claims, characterized in that they correspond to at least one of the following formulas in which mean
VH, CH₃, OCH₃, OC₂H₅ or NHAcyl, in particular NH-CO-CH₃,
p, m are independently 0 or 1,
RH or C₂H₅,
W, Y are independently CH = CH₂ or CH₂CH₂OSO₃H and
Z is H, CH₃ or OCH₃. 5. A reactive dye according to at least one of the preceding claims, characterized in that they correspond to one of the following formulas. 6. A process for the preparation of the reactive dyes according to claim 1 by diazotization of amines D-NH₂ and coupling the resulting diazonium compounds with aminonaphtholsulfonic acid derivatives of the formula 7. Compounds of the formula in which mean
m, n are independently 0 or 1,
Y is CH = CH₂, CH₂CH₂OSO₃H or CH₂CH₂Cl,
R is H or C₁-C₃alkyl which may be substituted by OH, CO₂H or CN,
Z is H, C₁-C₄-alkyl or C₁-C₄-alkoxy. 8. Method of dyeing or printing natural and synthetic OH and / or amide group-containing Materials in which one has a dye Apply the material or incorporate it into the material and him, if necessary in the heat and / or in the presence of an acid-binding agent, fixed, characterized in that as color fabric used a dye according to claim 1.