DE3046451A1 - "HALO-TRIAZINYL COMPOUNDS, THEIR PRODUCTION AND USE" - Google Patents

Description

150-4343

Halo-Triaziny! Compounds, their preparation and use The invention relates to compounds of Fonsei I,

Hydrogen or sulfo,

R ₂ hydrogen, (t-4C) alkyl or 2-, 3- or 4-I-hydroxy- (2-4C) alkyl, R (i-4C) alkyl ₅ 2-, 3- or 4-hydroxy- (2 -4C) alkyl, HO ₃ S- (1-4C) alkyl, HOOC- (1-4C) alkyl or phenyl, the 1 to 3 substituents from the series sulfo, carboxy, halogen, (1-4C) alkyl and (1-4C) alkoxy can carry, mean or

R_ and R, together with the N atom to which they are attached, form a 6-membered heterocyclic ring which can contain a further hetero atom, where, if - ^ Ro ^R 3 ^for P " ⁵¹¹ ^ ³¹¹ ^ ¹ " ¹⁰ stands, R ^ means hydrogen.

R _{4 is} hydrogen or (1-4C) alkyl

Hai mean fluorine, chlorine or bromine,

their mixtures and salts thereof.

preferably represents hydrogen.

If R is hydrogen, the sulfo group in ring A is preferably in position 4 or 5, in particular in position 4; If R. denotes sulfo, the two sulfo groups preferably occupy the 4,6-position. R ₂ or R ₃ as alkyl is preferably methyl or ethyl, in particular methyl; R ₂ or R ₃ as hydroxyalkyl is preferably 2-hydroxyethyl or 2- or 3-hydroxypropyl, in particular 2-hydroxyethyl. R ₃ as sulfo- or carboxy-containing alkyl preferably represents HO S- or HOOC- (I or 2C) alkyl, particularly preferably HO S- or HOOC-C H-.

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S-

Contain alkyl or alkoxy substituents of the phenyl radical defined for R " preferably 1 or 2 carbon atoms and are in particular methyl or Methoxy; Halogen as a phenyl substituent represents fluorine, chlorine or bromine, preferably chlorine or bromine and in particular chlorine.

R as substituted phenyl preferably has 1 or 2 substituents substituted from the series sulfo, carboxy, chlorine, methyl and methoxy Phenyl; more preferably 3- or 4-sulfophenyl, the additional Substituents chlorine, methyl, methoxy, carboxy or sulfo, of which in particular Can carry methyl or sulfo, which is preferably in position 2 next to the sulfo group in position 4 or 5.

If R 1 and R together with the N atom form a heterocyclic ring, then this preferably represents a piperidine or morpholine ring.

R "preferably denotes R 'as hydrogen, methyl, ethyl, hydroxyethyl or 2- or 3-hydroxypropyl or R 'together with R' forms and the N atom is a piperidine or morpholine ring; more preferably R ″ as hydrogen, methyl or hydroxyethyl and very particularly preferably hydrogen.

R ~ preferably represents R 'as methyl, ethyl, hydroxyethyl, 2- or 3-hydroxypropyl, sulfo- or carboxy- (1-2C) alkyl-, phenyl or by 1 or 2 substituents from the series sulfo, carboxy, chlorine, Methyl and methoxy substituted phenyl or R 'together with R' and the N atom form a piperidine or morpholine ring; more preferably for R ~ as methyl, hydroxyethyl, sulfo- or carboxyethyl, phenyl, 3- or 4-sulfophenyl or for sulfophenyl which is further substituted by chlorine, methyl, methoxy, carboxy or sulfo; more preferably for RIP as hydroxyethyl, phenyl, 3- or 4-sulfophenyl, 2-methyl-4-sulfophenyl or 2,5-disulfophenyl; particularly preferred for R ' ^v as hydroxyethyl, 3- or 4-sulfophenyl, 2-methyl-4-sulfophenyl or 2,5-disulfophenyl and very particularly preferred for RV, as 3- or 4-sulfophenyl, 2-methyl-4- sulfophenyl or 2,5-disulfophenyl.

R, as alkyl preferably represents methyl or ethyl, in particular represents Methyl. R, preferably represents Ri as hydrogen or methyl, in particular for hydrogen.

Hal preferably denotes fluorine or chlorine, particularly preferably chlorine. Preferred compounds of the formula I are _{those in which (1) R 1} and the sulfo group in ring A are those given above

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take up preferred positions;

(2) R, for R! and in particular represents hydrogen;

(3) Hai is fluorine or chlorine;

(4) R "stands for R 'and R- stands for R';

(5) those of (4) wherein R "represents R" and R "represents R";

(6) those of (5), wherein R ~ is R "¹;

(7) those of (6), wherein R «is hydrogen and R 1 is Rl ^v ;

(8) those from (1) to (7), wherein Hai is chlorine;

(9) those from (l) to (S), in which, when R ~ is sulfophenyl, R. Means hydrogen;

(10) those from (1) to (8), wherein R. is hydrogen;

(11) those of the formula Ia,

NHR:

SO ₃ H

and their salts.

The nature of the cation of the sulfo groups and any additional ones that may be present Carboxyl groups are not a critical factor, but can be anything that is customary in the chemistry of reactive dyes act not a chromophoric cation, for example an alkali metal! on or unsubstituted or substituted ammonium ion. Examples of suitable Cations are lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetramethylammonium, triethylammonium and mono-, di- and triethanolammonium.

Preferred cations are the alkali metal ions including ammonium, Of these, sodium is particularly preferred.

The compounds of the formula I are prepared according to the invention by one is a copper-containing monoazoamino compound of the formula

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which can be in the form of the free acid or as a salt, or a Geraisch of it,

with a compound of the formula

or a mixture thereof
implements,

wherein either R is a radical of the formula (a) χ

(a)

ai

and R is hydrogen

or R is hydrogen and
χ

R is a radical of the formula (a) and is optionally converted into the salts.

However, the compounds of the formula I are preferably prepared by Implementation of the copper-containing monoazoamino compound of the formula II, in which R denotes hydrogen, with the amine of the formula III, in which R is a radical of formula (a) if the amine of formula III is a water-solubilizing agent Group contains. The condensation of the compound of the formula II with the compound of the formula III is carried out according to a method known per se carried out, preferably at temperatures between room temperature and 65 ° C. Sodium carbonate, sodium bicarbonate, sodium hydroxide, for example, can be used as acid-binding agents for the condensation steps or triethylamine can be used.

The compounds of the formulas II and III in which R and R are hydrogen

χ y

mean, are known or can be prepared by methods known per se will.

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Likewise, the compounds of the formulas II and III, in which R or R is a radical of the formula (a), can be prepared by methods known per se by condensation of the corresponding Compound in which R and R are hydrogen, with cyanuric halide. This condensation takes place according to methods known per se. For example, the chlorine atom is preferably replaced at temperatures from 0 to 5 ° C. The compounds of the formula I can be isolated in a manner known per se be performed; For example, the compounds can be separated out, filtered off and removed from the reaction mixture by the usual salting out with alkali metal salts be dried in vacuo.

The compounds of the formula I according to the invention and mixtures thereof represent Reactive dyes are, they are suitable for dyeing, padding and printing of organic substrates containing hydroxyl groups and nitrogen. As preferred Substrates are leather and textile materials made from natural or synthetic Polyamides, such as wool, silk or nylon, and in particular of natural or regenerated cellulose, such as cotton, viscose or zelwool or contain them.

The dyes of the formula I can be added to dye liquors or printing pastes all dyeing and printing processes customary for reactive dyes are used, both as a self-dyestuff and as a combination element.

The dyes according to the invention are very extensive, they have a good one Build-up capacity and remarkable fastness to use. They show balanced Fixing properties combined with high fixing yield.

The dyeings and prints obtained show remarkable light (especially Wet light) and wet fastness properties such as washing, water and perspiration fastness as well as chlorine fastness. In addition, they are not very sensitive to oxidation and, for example resistant to peroxide bleach. -

For the print shop, the clear state of the contours, the high washability and printing paste stability. For use according to the block method is the solubility and padding liquor stability of the invention Dyes are advantageous, with the level of fastness and washability in this case as well can be highlighted.

In the following examples, parts are parts by weight and percentages Weight percent; the temperatures are given in degrees Celsius.

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example 1

94.5 parts of 2-amino-1-hydroxybenzene-4-sulfonic acid are dissolved in 300 parts of water stirred and, after the addition of 15 parts of 30% hydrochloric acid, diazotized with 127 parts of 4N sodium nitrite solution at 0-5 ° within 60 minutes.

167.5 parts of 1-amino-8-hydrox3'naphthalene-3,6-disulfonic acid are used in 625 parts Stirred water and dissolved with the addition of sodium hydroxide solution at pH 6.5. After addition of 50 parts of sodium bicarbonate and 46 parts of sodium chloride and, after adding ice, the above diazo solution at 3-6 ° slowly over the course of about 90 minutes. The coupling genius will last 6 hours Stirred 3-6 °, then the temperature is allowed to rise gradually to 20 °. The monoazo dye formed is at pH 7 by sprinkling Salted out 310 parts of sodium chloride and filtered off.

This dye paste is in 900 parts of water and 45 parts of 30% strength Sodium hydroxide solution. 420 parts of a 1 molar copper sulfate solution are added dropwise at 50-60 ° over a period of 2-3 hours, while the pH becomes 3.0% strength Caustic soda kept at 5.

84.5 parts of sulfanilic acid are dissolved in 550 parts of water at pH 7. These The solution is allowed to drop within one hour at 0-5 ° to an initial charge of 87.5 parts of cyanuric chloride and 140 parts of a water-ice mixture. The pH becomes kept at 3-4 with 20% soda solution.

The solution of the coppered dye prepared above is presented and the sulfanilic acid-cyanuric chloride condensate was slowly added dropwise, the Reaction temperature is gradually increased to 40-45 °. The pH is kept at 5-6 with 20% soda solution. Before the final isolation one sets to pH 7 and clears with a little activated charcoal. The dye is then salted out at 40 ° with 800 parts of sodium chloride, filtered at 30 ° and dried, it corresponds to the formula

SO ₃ Na

SO ₃ Na

With this dye, natural and regenerated cellulose in red

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dyed or printed in bright violet shades. The dyeings and prints show in particular good light and wet fastness properties as well as good chlorine fastness properties.

Example 2

86.5 parts of sulfanilic acid are added to 500 parts of water at pH 4.5 dissolved by sodium hydroxide solution. The diazotization is then carried out as in Example 1.

A filtered solution of 189.5 parts of 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid (in the form of the potassium salt) in 750 parts of water is cooled and adjusted to pH 6.5. The above diazo suspension is within an hour pumped in at approx. 8 °, the pH being kept at 6.5 with soda solution. Most of the dye that forms precipitates out. One dilutes through Add water to 3000 parts by volume and leave overnight at room temperature stir.

The dye suspension obtained is 500 parts of a 1 molar Copper sulfate solution and mixed with 50 parts of sodium acetate. Be at 15 ° firstly 90 parts of sodium perborate are sprinkled over the course of 2 hours, then 40 parts of a 30% strength hydrogen peroxide solution are added dropwise over the course of one hour. It is gradually warmed to 40 ° and stirred for 3 hours at 40 °. The copper-containing dye is 500 parts at room temperature Sodium chloride and 2500 parts of methanol precipitated and filtered off. The dye paste obtained is adjusted to 1000 parts by volume mixed with water. The acetyl group is split off by hydrolysis for 4 hours at 60 ° with 50 parts of solid sodium hydroxide. For isolation is adjusted to pH 5, the dye by sprinkling in 225 parts of sodium chloride precipitated and filtered at 40 °.

The dye paste is again mixed with water with a setting of 1000 Volura parts touched. Then, by sprinkling on approx. 50 parts of cyanuric chloride condensed within about 5 hours at 0-5 °, the pH being kept at 5 with soda solution.

The dye solution obtained in this way is added dropwise at 60 ° within about 4 hours a solution of 56.1 parts of 1-amino-2-methylbenzene-4-sulfonic acid in 450 parts of water. The pH of the solution is kept at 5 with soda. The forming Dye gradually precipitates. The pH is adjusted to 6.5 and the dye is filtered off.

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The pressed dye is at 50 ° in water with a setting of 1500 Volume parts solved. The solution is made with the addition of some activated charcoal Clarified by filtration, then the dye is precipitated by adding 150 Divide sodium chloride, filter and dry. The dye corresponds the formula

it dyes and prints natural and regenerated cellulose with a bluish tinge purple tones. The dyeings and prints obtained show good wet fastness properties and good chlorine fastness properties.

Further compounds of the formula I can be prepared analogously to Example 1 or 2 for which R, denotes hydrogen and the other variables are listed in Tables 1 and 2 below. The dyes produced in this way are depending on the manufacturing and isolation conditions as Sodium salts. With these dyes, cellulose fibers can be produced for a long time by one of the processes known to be suitable for reactive dyes or short liquor can be colored or printed. Dyeings and prints show good light and wet fastness properties as well as good chlorine fastness properties. For the In the dyes listed in the tables, the shade of the dyeing on cotton is given in the last column J, which corresponds to a = reddish purple

b = bluish purple

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Table 1

Example No.

Position SO Na in ring A

^R i
(Position) Hal II Cl H Cl H Cl H Cl H F. H Cl H Cl H Cl H F. H Cl H Cl H Cl H F. SO Na (6) ^: Cl H Cl do. Cl do. Cl do. Cl do. Cl do. Cl

3 4 5 6

10 11

12 13

14th

15th

16 17 18

19 20

21 22

4 4 4 4

4 4

5 5

4 5 4

H H

CIL

H H

H H H H

H II

CH,

-SO Well

SO ₃ Na

-CH ₂ CH ₂ SO ₃ Na

CH,

SO ₃ Na

do.

do.

CH "

VSO ₃ Na

b b b b

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Table 2

Example No. position
SO well im
Ring A (Position) Shark ^NXr 3 J 23 4th H Cl / CH - CH \
-N CH ₂ a 24 5 H Cl do. b 25th 4th H Cl -N ^{2 2} ^ O a 26th 4th SO ₃ Na (6) Cl do. b

Possible applications of the reactive dyes according to the invention are in illustrated by the following rules.

Dyeing instructions A

2 parts of the dye from Example 1 are warm in 100 parts Water (approx. 40 °), to which 10 parts of urea were added, dissolved. Another 30 parts of a 10% sodium carbonate solution and 0.5 part of 1-nitrobenzene-3-sulfonic acid are added Sodium too. A cellular wool fabric is impregnated with this solution in such a way that it absorbs 75% of its dry weight in dye solution. After drying, the fabric is steamed for 5 to 10 minutes at 102 °, then rinsed and soaped at the boil for 15 minutes. Receives after drying one has a reddish violet dyeing with good light and wet fastness properties as well as chlorine chloride.

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Dyeing instruction B

2 parts of the dye from Example 7 are mixed with 50 parts of "water" and 20 parts of urea dissolved at 20 °. After adding 15 parts of a 10% Sodium carbonate solution, the dye solution is made up to 100 parts by volume. The solution obtained is padded onto 20 parts of cotton fabric so that the Liquor pick-up of the fabric is 80% of its dry weight. The padded fabric is first toe-dried, then steamed for 10 minutes at 103 °. The dye is rinsed, soaped at the boil, rinsed again and then dried. A reddish purple color is obtained Coloring with a good level of fastness.

Printing regulation Ct

Mercerized cotton sateen is made with a printing paste of the following composition

25 parts of the dye from Example 1

100 parts of urea

440 parts of water

400 parts of a 4% sodium alginate thickener

10 parts of sodium l-nitrobenzene-3-sulfonic acid

25 parts sodium bicarbonate

printed according to the usual method.

The printed textile material is steamed for 4-8 minutes at 102-104 ° and then Rinsed cold and warm. After hot soaking, followed by renewed rinsing and drying, a reddish purple color is obtained Print with good light and wet fastness properties as well as chlorine fastness properties.

These dyeing and printing instructions are available with the dyes mentioned representative of the other representatives listed in the example section.

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Claims (7)

Case 150-4343 SANDOZ-PATENT-GMBH 7850 Lörrach Halo-triazinyl compounds, their production and use, patent claims 1.) Compounds of the formula Cu R hydrogen or SuIfο / Ii, hydrogen, (1-4C) alkyl or 2-, 3- or 4-hydroxy- (2-4C) alkyl R ₃ (1-4C) alkyl, 2-, 3- or 4-hydroxy- (2-4C ) alkyl, HO ₃ S- (1-4C) alkyl-, HOOC- (1-4C) alkyl- or phenyl, the 1 to 3 substituents from the series sulfo, carboxy, halogen, (1-4C) alkyl and (1 -4C) alkoxy can carry, mean or 2 and R "together with the N atom to which they are attached form a 6-membered heterocyclic ring which can contain a further heteroatom, where, when ~ NR ~ R" stands for p-sulfanilino, R. is hydrogen ,
Hydrogen or (1-4C) alkyl ^R 4
and Hai mean fluorine, chlorine or bromine,
their mixtures and salts thereof. 2. Process for the preparation of compounds of formula I according to claim 1 or mixtures thereof, characterized in that one copper-containing monoazoamino compound of the formula 130035/0586 3046A51 - 2 - 150-4343 O CHR _x II, which can be in the form of the free acid or as a salt, or a Mixture of them with a compound of the formula RyNR ₂ R ₃ in or a mixture thereof implements, wherein either R is a radical of the formula (a) 2t Hal and R is hydrogen or R is hydrogen and
χ R is a radical of the formula (a) and optionally converted into the salts. 3. Use of the compounds of the formula I or mixtures thereof according to claim 1 for dyeing, padding or printing textile materials, which consist of or contain natural or synthetic polyamides or natural or regenerated cellulose. 4. Use of the compounds of the formula I or mixtures thereof according to claim 1 for dyeing leather. 130035/0586 - 3 - 150-4343 5. Process for dyeing, padding or printing textile material! s which consist of or contain natural or synthetic polyamides or natural or regenerated cellulose, characterized in that dyeing, padding or printing is carried out with a compound of the formula I or a mixture thereof according to claim 1. 6. A process for dyeing leather, characterized in that with a compound of the formula I or a mixture thereof according to Claim 1 colors. 7. The colored or printed according to claim 5 or 6 Materials. 130035/0586