DE3826060A1 - Disazo class reactive dyes - Google Patents

Abstract

Disazo class reactive dyes of the general formula <IMAGE> and of the formula <IMAGE> where the substituent meanings are as defined in the description, are highly suitable for dyeing and printing OH- and NH-containing materials. They produce light- and wet-fast brilliant dyeings and prints.

Description

The present invention relates to disazoreactive dyes the general formula

wherein

in which
R = H, optionally substituted C₁-C₄ alkyl or XY,
X = divalent aliphatic radical and
Y = COOH, SO₃H or OSO₃H,
Z = H, CH₃, C₂H₅, OCH₃, OC₂H₅, NHCOC₁-C₄-alkyl, OH
and the benzene ring B can contain customary substituents.

The alkyl radical R can be straight-chain or branched. Examples of substituents of R are OH, OCH₃, OC₂H₅, Cl, CN.

The divalent aliphatic radicals X can be heteroatoms or heteroatom groupings, for example:

Examples of substituents of the benzene ring B are Cl, CH₃, OCH₃, OC₂H₅.

Suitable radicals R are, for example:

-CH₃, -C₂H₅, -n-C₃H₇, -iso-C₃H₇, -CH₂-CH₂-OH, -CH₂-CH₅-Cl, -CH₂-CH₂-CN

Suitable radicals X are, for example:

In the context of the formula (1), dyes are preferred, in to them

• 1) A = A₁, where wherein
  R₁ = -H, -C₁-C₄-alkyl, -X₁-Y
  X₁ = divalent, at most 6C atoms containing aliphatic radical, the may contain
• 2) A = A₂, where wherein
  R₂ = -H, -CH₃, -C₂H₅, -CH₂-CH₂-Y
  X₂ = -CH₂-, -CH₂CH₂-,
• 3) A = A₃, where wherein
  R₃ = -H, -C₁-C₄-alkyl, -X₁-SO₂-CH₂-OSO₃H.

Furthermore, dyes of the formula (1) are preferred in which 1-hydroxy-6-amino-naphthalene-3-sulfonic acid is used as a coupling component. In particular preferred are those dyes in which the Diazo component of the formula

stands.

The invention further relates to methods for Preparation of the dyes of the formula (1).

1) A disazo dye of the formula

is first with 2,4,6-trifluorotriazine with elimination condensed by hydrofluoric acid and the resulting Difluoro compound with an amine formula

with elimination of hydrofluoric acid to a dye Formula (1) implemented.

2) An aminohydroxynaphthalenesulfonic acid of the formula (5)

is condensed with 2,4,6-trifluorotriazine with elimination of hydrofluoric acid and the resulting difluoro compound reacted with an amine of formula (4). The coupling component of the formula obtained

becomes a with a diazo component of the formula (2) Dye of the formula (1) combined.

3) An amine of formula (4) with 2,4,6-trifluorotriazine with elimination of hydrofluoric acid to a Difluoro compound of the formula (7)

condensed and this with a coupling component of the Formula (5) to a compound of formula (6) with elimination implemented by hydrofluoric acid and then this coupled with a diazo component (2).

The condensation of the compounds of the formula (3), (4) and (5) with the 2,4,6-trifluorotriazine is preferably done in aqueous solution or suspension at low Temperature and preferably at about 0 ° C and at weakly acidic, neutral to weakly alkaline pH. The hydrogen fluoride released is added aqueous alkali metal hydroxides, carbonates or bicarbonates dulled. Implementation of the difluoro compounds with the corresponding reactants also take place preferably in aqueous solution or suspension low temperature preferably at 0 to 20 ° C and at weakly acidic to weakly alkaline pH.  

The acylation of (3) is generally carried out using Na or K salts. It turns out to be particularly favorable - In particular in the case that B only one sulfo group contains - the use of a mixed Li-Na or Li-K salt of (3), which is based on the betaine

and neutralization with 1 mol of Li base.

The one in the condensation of (3) with trifluorotriazine liberated hydrogen fluoride is generally preferred intercepted by Li bases, for example LiOH.

The dyes of the formula (3) are obtained by coupling of diazotized amines of the formula (2) with the N-acylated Coupling components of formula (5) in the weak acidic to weakly alkaline range. The acyl residue is then by heating with acids or alkalis cleaved. Examples of an acyl radical are acetyl or carbamoyl.  

Examples of diazo components of the formula (2) are the following

Coupling components of formula (5) are: 1-hydroxy-6-aminonaphthalene-3-sulfonic acid and 1-hydroxy-7-amino-naphthalene-3-sulfonic acid.  

Examples of amines of formula (4) are the following:

The invention further relates to dyes formula

where R₄ = H, CH₃, C₂H₅, the benzene ring B may have customary substituents and Z = H, CH₃, C₂H₅, OCH₃, OC₂H₅, NHCOC₁-C₄-alkyl, OH,
in particular dyes of the formula

These dyes are produced analogously to the dyes (1) and have similar properties.  

The new dyes give on cellulose as well as natural or synthetic polyamide materials clear colorations. They are characterized by high color strength.

The new ones are found as water-soluble reactive dyes Dyes preferred interest for dyeing textile materials containing hydroxyl and amide groups, especially of materials from native and regenerated Cellulose and synthetic polyamide and Polyurethane fibers, wool and silk.

The materials mentioned are after those for water-soluble Reactive dyes generally known and in the usual technology dyed or printed. Light and wet fast brilliant dyeings are then obtained and prints.

The temperature data in the examples are ° C. The formulas of water-soluble reactive dyes in the description and in the examples that of free acids. They are isolated and applied Dyes in general in the form of their alkali salts, especially the lithium, sodium or potassium salts.

Obtain the color codes given in the examples on the Color Index Hue Indication Chart (Indicator Numbers).  

example 1

0.1 mole of the dye of the formula

are stirred in 1 l of water and by adding 0.1 mol of LiOH dissolved neutral. Then you throw 500 g of ice and then drops in 13.5 g of trifluorotriazine, the hydrofluoric acid released by LiOH solution is dulled. After condensation is allowed to Run in 0.1 mol of N-methyl taurine in aqueous solution. The Exchange of the second fluorine atom takes place at pH 8.5-9 and 0 ° to 5 °, likewise the hydrofluoric acid released is neutralized by lithium hydroxide. The dye is by salting out with 25 volume percent potassium chloride deposited. After suction, drying and grinding a red dye powder which is readily soluble in water is obtained.

The dye corresponds to the formula

It dyes cotton according to one of the reactive dyes usual procedures in clear yellowish red tones (Color code 7).

In this example, N-methyl taurine is replaced by the the amines mentioned below are also obtained readily water-soluble reactive dyes, cotton turn yellowish red.

Methylaminomethanesulfonic acid
Ethylaminomethanesulfonic acid
Taurine
Amino acetic acid
Methylaminoacetic acid
Aminolsulfate = β- sulfatoethylamine
N-methyl-N- β- sulfatoethylamine
β- sulfatoethyl- β ′ -aminoethyl sulfone
b -Sulfatoethyl- β '-sulfatoethyl amine

You can also get valuable examples if you read from the aminodisazo dyes listed below and the amines used in the example for the exchange of the second fluorine atom

Color on cotton yellowish red 7  

Claims (6)

1. Disazoreactive dyes of the general formula wherein in which
R = H, optionally substituted C₁-C₄ alkyl or XY,
X = divalent aliphatic radical and
Y = COOH, SO₃H or OSO₃H,
Z = H, CH₃, C₂H₅, OCH₃, OC₂H₅, NHCOC₁-C₄-alkyl, OH
and the benzene ring B can contain customary substituents. 2. Dyes of claim 1 with
A = A₁, where wherein
R₁ = -H, -C₁-C₄-alkyl, -X₁-Y
X₁ = divalent, at most 6C atoms containing aliphatic radical, the can contain
such as
A = A₂, where wherein
R₂ = -H, -CH₃, -C₂H₅, -CH₂-CH₂-Y
X₂ = -CH₂-, -CH₂-CH₂-,
and
A = A₃, where wherein
R₃ = -H, -C₁-C₄-alkyl, -X₁-SO₂-CH₂-CH₂-OSO₃H. 3. Dyes of claims 1 and 2 of the formula 4. Dyes of the formula wherein
Z = H, CH₃, C₂H₅, OCH₅, OCH₃, OC₂H₅, NHCOC₁-C₄-alkyl, OH, R₄ = H, CH₃, C₂H₅ and B may have conventional substituents. 5. Use of the dyes of claims 1 to 4 for Dyeing and printing of OH- and NH-containing materials, especially textile materials. 6. Colored with the dyes of claims 1 to 4 or printed OH- or NH-containing materials.