DE3835724A1 - New reactive azo dyes - Google Patents

Abstract

Azo dyes of formula (Ia-If) and their salts are new: R1 = H or 1-4C alkyl; Z = 2,6-dichloro-5-cyano-4-pyrimidinyl or 4,6-dichloro-5-cyano-2-pyrimidinyl; D1 = e.g. a gp. of formula (a) or (b): R2 = H, halogen, 1-4C alkyl, 1-4C alkoxy, acetamido, benzamido or COR7; R3 = H, halogen, 1-4C alkyl, 1-4C alkoxy or COR7; A1 = 2-3C alkylene; R4 = H, SO3H, 1-4C alkyl or 2-4C hydroxyalkyl; R5 = H, 1-4C alkyl or 1-4C alkoxy; R6 = H, halogen, 1-4C alkyl, 1-4C alkoxy, 2-5C alkanoamido or ureido; R7 = OH, 1-4C alkoxy or NH2; p = 0-2; r = 1 or 2; Q1 = H, 1-4C alkyl, 5-6C cycloalkyl, Ar1, Ar1(1-4C)alkyl, COR7, 1-4C sulphoalkyl, 1-4C sulphatoalkyl or R7CO(1-4C)alkyl; Ar1 = phenyl opt. substd. by 1-3 of 1-4C alkyl, 1-4C alkoxy, halogen, COOH and SO3H; Q2 = H, CN, NO2, SO3H, COR7, 1-4C alkyl (opt. monosubstd. by OH, halogen, CN, 1-4C alkoxy, Ar2, SO3H, OSO3H, COR7 or NH2), SO2NH2, Ar2 or R10-substd. 1-pyridinio; Ar2 = phenyl substd. by R8 and R9; R8 = H, halogen, 1-4C alkyl, 1-4C alkoxy, COOH or SO3H; R9 = H, SO3H or NR1Z; R10 = H, 1-4C alkyl or 2-4C hydroxyalkyl; Q3 = H, Y1NR1Z, 1-6C alkyl, 2-4C alkenyl, 2-4C alkynyl, 5-6C cycloalkyl, Ar3, Ar3(1-4C)alkyl, Y2(1-6C)alkyl or Q4(2-4C)alkyl; Y1 = 2-6C alkylene (opt. interrupted by O or NR1), monohydroxy-substd. 3-6C alkylene, Ar4NR1Z, A2Ar4NR1Z or Ar4A2NR1Z; Ar3 = phenyl substd. by NR1Z or by 1-3 of halogen, 1-4C alkyl, 1-4C alkoxy, SO3H, COOH and NH2; Y2 = COOH, 2-5C alkoxycarbonyl, SO3H, OSO3H, OH, CN, 1-4C alkoxy, NH2, a protontable aliphatic, alicyclic, aromatic or heterocyclic amino gp. or a quat. ammonium gp.; Q4 = 4-Z-1-piperazinyl; Ar4 = phenylene opt. monosubstd. by SO3H; A2 = 1-4C alkylene; t = 2 or 3; R16 = H or SO3H; m = 0 or 1 such that m+r = 2 or 3; provided that (a) (Ia) contains 1 or 2 Z gps., and (b) the O and azo gps. in (If) are bonded to the 1,2 or 2,1 posns. of the naphthyl ring.

Description

The invention relates to fiber-reactive 1: 1 copper complex monoazo compounds, Process for their preparation and their use as reactive dyes in dyeing and printing processes.

The invention accordingly relates to compounds of the formula I

wherein
one of the radicals R₁ and R₂ for -SO₃H and the other for group (a)

and
R₃ is hydrogen or C _1-4 alkyl,
and their salts.

In compounds of the formula I, R₁ preferably denotes group (a); continue preferably in group (a) R₃ is hydrogen or methyl, in particular for hydrogen.

The nature of the cation of the sulfo groups in compounds of the Formula I, if they are in salt form, is not critical Factor, but it can be any, in the chemistry of Reactive dyes act usual non-chromophoric cation. requirement is, however, that the corresponding salts are the condition of Meet water solubility.  

Examples of suitable cations are alkali metal ions or unsubstituted or substituted ammonium ions, such as lithium, sodium, Potassium, ammonium, mono-, di-, tri- and tetramethylammonium, triethylammonium and mono-, di- and triethanolammonium. Preferred cations are the alkali metal ions and ammonium, especially of these sodium is preferred.

In general, in a compound of formula I, the cations of Sulfo groups may be the same or different and a mixture of the above Represent cations, d. H. the connection can also be mixed Salt form.

The present invention further includes a method of making of the compounds of formula I, characterized in that a compound Formula II,

wherein
one of the radicals R₄ and R₅ for -SO₃H and the other for -NHR₃, and
R₃ is hydrogen or C _1-4 alkyl,
reacted with 5-cyano-2,4,6-trichloropyrimidine.

The reaction of a compound of formula II with 5-cyano-2,4,6-trichloropyrimidine is conveniently carried out at 0 ° -40 ° C and pH 7-9; as The reaction medium is normally water, 5-cyano-2,4,6-trichloropyrimidine but can also be dissolved in an organic solvent, for example acetone.

The isolation of the compounds of the formula I can be known per se Done wisely; e.g. B. can the compounds directly or by conventional Salting out with alkali metal salts separated from the reaction mixture,  filtered off and dried (in vacuo) at a slightly elevated temperature will.

Depending on the reaction and isolation conditions, a Compound of formula I as free acid or preferably in salt form or obtained as a mixed salt and then contains, for example, one or several of the above cations. Salts or mixed salts can but also produced starting from the free acid in a conventional manner and vice versa or it can also be a conventional one Salting can be made.

The starting compounds of formula II are either known or they are can be analogous to known methods from known starting materials be preserved.

The compounds of formula I and mixtures thereof are reactive dyes dar; they are suitable for dyeing or printing hydroxy group or nitrogenous organic substrates. As preferred substrates These include leather and fiber materials made from natural or synthetic materials Polyamides and especially from natural or regenerated ones Cellulose, such as cotton, viscose or cellulose exist or contain them. The most preferred substrate is textile material made of cotton exists or contains them.

The compounds of the formula I can be used in dyeing liquors or in printing pastes by all dyeing or printing processes customary for reactive dyes be used. Preference is given to the pull-out process in the temperature range colored from 30-60 ° C.

The compounds according to the invention can be used as a single dye or because of their good combinability also as a combination element with other reactive dyes of the same class, the comparable dye Properties e.g. B. regarding general fastness properties, extract value etc., are used. The combination stains obtained show just as good fastness properties as the dyeings with single dye.  

With the compounds of the formula I there are good pull-out and fixing values receive. The unfixed dye can be easily washed out. The dyeings and prints obtained show good lightfastness. They also have good wet fastness properties such. B. regarding Wash, water, sea water and sweat fastness and have good resistance against oxidative influences such as chlorine-containing Water, hypochlorite bleach, peroxide bleach and perborate Detergents.

The following example serves to illustrate the invention. By doing Example means parts by weight or volume and percentages by weight or volume percent; the temperatures are given in degrees Celsius.

example

123 parts (0.5 mol) of 6-acetylamino-2-amino-1-hydroxybenzenesulfonic acid are in 250 parts of water and 250 parts of ice with the addition of 40 parts 30% hydrochloric acid stirred and at 0 ° C to a maximum of + 5 ° C by slow Add 125 parts of 4N sodium nitrite solution diazotized. Subsequently the small excess of nitrite is destroyed with a little sulfamic acid.

125 parts of 1-hydroxynaphthalene-3,6-disulfonic acid are added in 500 parts Dissolved water and cooled by adding 250 parts of ice. Subsequently the cooled diazonium salt solution is allowed to stir slowly flow in and let stir for about an hour. During the coupling reaction is the pH of the reaction mixture by continuous Adding caustic lime kept between 11.5 and 12.5.

The resulting solution of the coupling product is then heated to 50 ° and over 30 minutes with a solution of 125 parts of copper sulfate pentahydrate added to 300 parts of water. The reaction product is insulated by salting out and filtering.  

The well-pressed nutsche residue is mixed with 50 parts of 30% sodium hydroxide solution stirred and then acidified with 120 parts of 30% hydrochloric acid. The mixture is stirred under reflux for 90 minutes, then is off the formed thick suspension of the copper complex of the aminomonoazo dye isolated by filtration. The residue is squeezed out well dried in vacuo at 80 ° C.

17.4 parts (0.03 mol) of the dye prepared above are added stirring well in 300 parts of water with a little 10% sodium hydroxide solution at pH 8 solved. To the solution, which is cooled to 14 ° with 100 parts of ice, 10.4 parts (0.05 mol) of 5-cyano-2,4,6-trichloropyrimidine with something Rinsed acetone. The spontaneously falling pH becomes during the condensation reaction kept at 7 with 20% soda solution, at the same time that Reaction mixture heated to 35 °. The pH remains after approx. 40 minutes almost stable, after a total of two hours of reaction becomes isolation the very fine suspension of the product is filtered off cold and the Residue dried in vacuo at approx. 40 °.

The dye of the formula obtained

dyes cotton or fibers from regenerated cellulose in ruby red Tones; the dyeings show good light and wet fastnesses as well as good ones Stability against oxidative influences.

The dye shows an absorption maximum λ _max = 536 nm; the value was determined in distilled water buffered to pH 7.

According to the method described above, the dye of Example obtained as the sodium salt. It can depend on the chosen one Implementation and isolation conditions or through subsequent Measures in a manner known per se in the form of the free acid or produced in another salt form or mixed salt form and then for example one or more of those in the description contain further cations.

Below are uses of the dye described illustrated.

Instructions for use A

In a dyebath containing 0.3 parts in 300 parts of demineralized water of the dye according to the example and 15 parts of Glauber's salt (calcined) contains, 10 parts of cotton fabric (bleached) are entered at 40 °. After 30 minutes at 40 °, the addition is carried out at intervals of 10 minutes of a total of 6 parts of soda (calcined), in portions of 0.2; 0.6; 1,2 and finally 4 parts, keeping the temperature at 40 ° becomes. The dyeing is then continued at 40 ° for one hour. Subsequently the dyed material is left in flowing cold for 3 minutes Water, then rinsed in running hot water for 3 minutes. The coloring is in 15 parts in 500 parts of demineralized water in the presence boiling of 0.25 parts of a commercially available anionic surfactant washed. After rinsing in running water (hot for 3 minutes) centrifuged and the color dried in a drying cabinet at approx. 70 °. A ruby red cotton dyeing of good fastness properties is obtained, in particular shows good light and wet fastness and is stable against oxidative influences.  

Application regulation B

A dye bath that demineralized 10 parts Glauber's salt (calcined) in 300 parts Contains water, 10 parts of cotton material (bleached) added. The bath is heated to 40 ° within 10 minutes, then 0.5 part of the dye according to the example is added. After a further 30 minutes at 40 °, 3 parts of soda (calcined) added, then continue at 40 ° for 45 minutes.

The colored material is washed with running cold water, then with hot Rinsed water and boiling in the same way as for regulation A. washed. After rinsing and drying, a ruby red cotton dyeing obtained which the properties listed for regulation A owns.

Instructions for use C

A printing paste with the ingredients

40 parts of the dye according to the example
100 parts of urea
350 parts of water
500 parts of a 4% sodium alginate thickener
10 parts of sodium bicarbonate
1000 pieces in total

is applied to cotton material using the usual printing processes.

The printed material is steamed at 102-104 ° C for 4-8 minutes and then rinsed cold and hot. Then the fixed cotton material washed at the boil (analogous to regulation A) and dried. The received one ruby red print shows good general fastness properties.

Claims (6)

1. Compounds of formula I wherein
one of the radicals R₁ and R₂ for -SO₃H and the other for and
R₃ is hydrogen or C _1-4 alkyl, and their salts. 2. A process for the preparation of compounds of formula I, defined in claim 1, characterized in that a compound of formula II, wherein
one of the radicals R₄ and R₅ represents -SO₃H and the other represents -NHR₃, and R₃ represents hydrogen or C _1-4 alkyl,
reacted with 5-cyano-2,4,6-trichloropyrimidine. 3. Process for dyeing or printing on or nitrogenous organic substrates, characterized in that one with a compound of formula I, defined in claim 1, or with Mixtures of these colors and prints. 4. The method according to claim 3, for dyeing or printing leather or of fiber materials made from natural or synthetic polyamides or consist of natural or regenerated cellulose or these contain. 5. The method according to claim 4, for dyeing or printing Textile material consisting of or containing cotton. 6. The dyed or printed according to any one of claims 3-5 Substrates.