CH643873A5 - MONOAZO COMPOUNDS WITH COPPER, METHOD FOR THE PRODUCTION AND THEIR USE. - Google Patents

Description

The invention relates to compounds of the For me s I,

—Cu— R., R

-Mvpn l.3

-UÖl

/ H SO V ^ <; n p SO_H 3 bü3H

3 years

where 2o

R, hydrogen sulfo or halogen (only in position 4), Ri hydrogen, (1-4C) alkyl or hydroxy- (2-4C) alkyl, Rj (1-4C) alkyl, hydroxy- (2-4C) alkyl, H03S - (1-4C) -alkyl-, HOOC- (1-4C) -alkyl- or phenyl, the 1 to 3 substituents from the series sulfo, carboxy, halogen, (1-4C) -alkyl 25 and (1- 4C) can carry alkoxy, mean or

R2 and Rj together with the N atom to which they are attached form a 6-membered heterocyclic ring which may contain a further heteroatom, and

R3 also stands for hydrogen if the 30 substitution 4-sulfo next to R, in the meaning of hydrogen, is excluded for ring A,

R4 is hydrogen or (1-4C) alkyl and shark are fluorine, chlorine or bromine, and their salts, with the restriction that a compound of the formula I, 35 contains the 2 sulfo groups in ring A in positions 4 and 6, in which R4 stands for hydrogen, shark for chlorine and -NR2R3 for p-sulfanilino are excluded from the scope, processes for their preparation and their use as dyes. 40

The compounds of formula I, which are excluded from the scope of protection as defined in claim 1 and in the description, are the subject of older, pre-published patents.

Ri as halogen means fluorine, chlorine or bromine, in particular chlorine.

R is preferably R / as hydrogen, chlorine or sulfo, more preferably for R 1 "as hydrogen or sulfo and particularly preferably for hydrogen.

If R is hydrogen, the sulfo group in ring A is preferably in position 4 or 5, in particular in position 4; means R | Halogen, the sulfo group is preferably in position 6; when R is sulfo, the two sulfo groups preferably occupy positions 4,6.

R4 as alkyl is preferably methyl or ethyl, 55 in particular methyl. R4 preferably represents R4 'as hydrogen or methyl, in particular hydrogen.

Shark preferably means fluorine or chlorine, particularly preferably chlorine.

R2 or R3 as alkyl preferably denotes methyl or 60 ethyl, in particular methyl; R2 or R3 as hydroxyalkyl is preferably hydroxyethyl or 2- or 3-hydroxypropyl, in particular hydroxyethyl.

R3 as sulfo- or carboxy-containing alkyl is preferably H03S- or HOOC- (1 or 2C) alkyl, particularly preferably ho3s- or HOOC-C2H4-. Alkyl or alkoxy substituents of the phenyl radical defined for R3 preferably contain 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.

R3 as substituted phenyl preferably denotes phenyl substituted by 1 or 2 substituents from the series sulfo, carboxy chlorine, methyl and methoxy; more preferred

3- or 4-sulfophenyl, which can carry chlorine, methyl, methoxy, carboxy or sulfo, in particular methyl or sulfo, as an additional substituent, which is preferably in position 2 next to the sulfo group in position 4 or 5.

If R2 and R3 form a heterocyclic ring together with the N atom, this is preferably a piperidine or morpholine ring.

R2 preferably denotes R2 'as hydrogen, methyl, ethyl, hydroxyethyl or 2- or 3-hydroxypropyl; more preferably R2 "as hydrogen, methyl or hydroxyethyl and very particularly preferably hydrogen.

R3 preferably represents R3 'as hydrogen, 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; more preferably for R3 "as hydrogen, methyl, hydroxyethyl, sulfo- or carboxyethyl, phenyl, 3- or 4-sulfophenyl or for sulfophenyl which is further substituted by chlorine, methyl, methoxy or sulfo; more preferably for R3" 'as hydrogen, hydroxyethyl , Phenyl, 3 or

4-sulfophenyl, 2-methyl-4-sulfophenyl or 2,5-disulfophenyl; particularly preferred for R3'v as hydrogen, hydroxyethyl, 3- or 4-sulfophenyl, 2-methyl-4-sulfophen-yl or 2,5-disulfophenyl and very particularly preferably for R3v as 3- or 4-sulfophenyl, 2-methyl -4-sulfophenyl or 2,5-disulfophenyl.

Furthermore, R2 and R3 also preferably denote as R2 'and R3' together with the N atom to which they are attached a piperidine or morpholine ring.

Preferred compounds of the formula I are those in which

(1) R represents R, ';

(2) those of (1) wherein Rj 'and the sulfo group in ring A occupy the preferred positions indicated above;

(3) R4 is R4 'and especially hydrogen;

(4) shark means fluorine or chlorine;

(5) R2 is R2 'and R3 is R3';

(6) those of (5) wherein R2 is R2 "and R3 is R3";

(7) those of (6), wherein R3 is R3 "';

(8) those of (7) wherein R2 is hydrogen and R3 is .3'v;

(9) those of (1) to (8) wherein shark is chlorine;

(10) those of the formula Ia,

643 873

4th

la and their salts, with the restriction that a compound of formula Ia, which contains 2 sulfo groups in ring A in positions 4,6 and R3V in the meaning of 4-sulfophenyl, is excluded from the scope.

The nature of the cation of the sulfo groups and any additional carboxyl groups present is not a critical factor, but can be any non-chromophoric cation common in the chemistry of reactive dyes, for example an alkali metal ion 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 which sodium is particularly preferred.

The compounds of the formula I are prepared according to the invention by, on the one hand, a cyanuric halide, each with the amount equivalent to the reaction of a halogen atom, of a copper-containing monoazoamino compound of the formula II,

35

SO ^ H

which can be in the form of the free acid or as a salt, on the one hand with the diazonium compound of an amine of the formula

25th

couples, on the other hand condenses with a cyanuric halide in such a ratio that only 1 halogen atom reacts, a halogen atom of the cyanuric halide against the amine of the formula at any time

HNR2R3

III

II

40

exchanged under condensation and metallized at any time during the individual process steps or as a final reaction with a copper-containing compound or b) the compound of the formula

R, / R2

: s? H - 1Tv X

II Nj ^ jN 3

R.- «ii v vi.

Shark which can be in the form of the free acid or as a salt, or a mixture thereof, on the other hand the amine component of the formula III

45

HNR2R3

III 50

or a mixture thereof, the reaction being independent of the order of addition of a compound of the formula II and III, and if appropriate converted into the salts.

Furthermore, the compounds of the formula I can also be prepared by a) regardless of the order of addition, the coupling component of the formula

IV

55

60

65

which can be in the form of the free acid or as a salt and in which Rs is hydrogen or (1-4C) alkoxy, or a mixture thereof in the case that R5 is (1-4C) alkoxy, by dealkylative coppering or in the case that R5 stands for hydrogen, is converted into the metal complex by oxidative coppering and a compound of the formula I thus obtained is optionally converted into the salt.

However, the compounds of the formula I are preferably prepared by reacting the copper-containing monoazoamino compound of the formula II with cyanuric halide and subsequent condensation with the amine of the formula III or also by reacting the compound of the formula II with the condensation product of cyanuric halide and amine of the formula III, if the latter contains a water solubilizing group.

The individual condensation steps are carried out according to methods known per se. The gradual replacement of the halogen atoms in the cyanuric halide is preferably carried out in a weakly acidic to weakly alkaline medium, for example the first chlorine atom is preferably exchanged at temperatures from 0 to 5 ° C., the second chlorine atom at an elevated temperature, preferably between room temperature and 65 ° C. As an acid-binding

5,643,873

Agents can e.g. Sodium carbonate, sodium bicarbonate, fastness to use. They show balanced fixation properties

Find sodium hydroxide or triethylamine. associated with high fixation yield.

Diazotization and coupling reaction, metallization The dyeings and prints obtained show remarkable

and dealkylating or oxidative coppering are carried out according to valuable light (especially wet light) and wet fastness properties, as methods known per se. 5 fastness to washing, water and perspiration as well as chlorine

Metallization with copper salt solution will be preferred. In addition, they are not very sensitive to oxidation and at temperatures of 40-80 ° C and weakly acidic pH (to make them resistant to peroxide bleach,

5). For the dealkylative coppering ar- For the printing house, the clear state of the contours is to be mentioned, which is advantageously processed with an ammoniacal copper-II- high washability and printing paste stability.

sulfate, acetate or chloride solution, optionally in counterions. For use according to the padding process, the presence of organic water-soluble bases such as alkylami- solubility and padding liquor stability of the inventive

Dyes, alkanolamines, pyridine or dimethylformamide dyes are advantageous, but in this case too

at temperatures of, for example, 80-100 ° C. The oxide level and washability are emphasized tive copper with copper salt solution in the presence of a can.

Oxidizing agent such as sodium perborate turns 15. In the examples below, parts preferably mean parts by weight in a temperature range of 10-50 ° C., the percentages being percentages by weight; the temperatures led. are given in degrees Celsius.

The compounds of the formula I can be isolated in a manner known per se; e.g. can they

Compounds by usual salting out with alkali metal salt 20 Example 1

zen separated from the reaction mixture, filtered off and 94.5 parts of 2-amino-l-hydroxybenzene-4-sulfonic acid

be dried in vacuo. stirred in 300 parts of water and after adding 15

The starting compounds are known or they can parts of 30% hydrochloric acid with 127 parts of 4N sodium nitrite

starting from known starting materials analogous to solution at 0-5 ° within 60 minutes.

known methods are produced. 25 167.5 parts of l-amino-8-hydroxynaphthalene-3,6-disulfone

When a compound of the formula II is prepared by acid, the mixture is stirred in 625 parts of water and

dealkylative or oxidative coppering must be dissolved in sodium hydroxide solution at pH 6.5. Intermediate to this solution group in the coupling component by dropwise addition of 50 parts of sodium bicarbonate

Acylation, preferably protected by an acetyl group, and 46 parts of sodium chloride and after the addition of ice. After the metallization has taken place, the protective group 30 of the above diazo solution is slowly added at 3-6 ° within about 90 minutes.

at an elevated temperature in an alkaline range. The coupling mixture is stirred for 6 hours at 3-6 °,

columns. then gradually let the temperature drop to 20 °

The compounds of formula I and according to the invention increase. The monoazo dye formed is at pH 7

Mixtures of these are reactive dyes, they are salted out by sprinkling 310 parts of sodium chloride and are suitable for dyeing, padding and printing with hydroxyl groups and filtered off.

and nitrogenous organic substrates. As preferred, this dye paste is in 900 parts of water and 45

Substrates are leather and textile materials made from natural parts of 30% sodium hydroxide solution. One leaves within 2-3

or synthetic polyamides such as wool, silk or hours at 50-60 ° 420 parts of a 1-molar copper sulfate solution.

Nylon, and especially from natural or regenerated solution; the pH is adjusted with 30% sodium hydroxide solution

Cellulose, such as cotton, viscose or rayon, are kept 40 at 5.

or contain them. 84.5 parts of sulfanilic acid are added in 550 parts of water

The dyes of the formula I can be dissolved in dye liquors or pH 7. This solution is left within an hour at 0-5 ° in printing pastes after all used for reactive dyes to give 87.5 parts of cyanuric chloride and 140

Coloring and printing processes are used, and parts of a water / ice mixture drip. The pH is used as a self-dye as well as a combination element. 45 20% soda solution kept at 3-4.

Dyes of the formula I which contain an unstable chlorine atom. The solution of the copper dyestuff prepared above is preferably introduced at temperatures between and the sulfanilic acid-cyanuric chloride con-

Colored 80 and 100 ° C; those which slowly add a labile fluorine atom while maintaining the reaction temperature are cold stainers and are therefore preferably increased gradually to 40-45 °. The pH is colored with 20% at temperatures between 20 and 40 ° C. The fixie 50 soda solution kept at 5-6. Before the final insulation is made with alkali, it is carried out in a manner known per se at pH 7 and clarified with a little activated carbon. The dye

80-100 ° C. is then at 40 ° with 800 parts of sodium chloride

The dyes according to the invention are very extensive, salted out, filtered at 30 ° and dried, which corresponds to that they have good build-up capacity and a remarkable formula

643 873

This dye is used to dye or print natural and regenerated cellulose in shades of reddish violet. The dyeings and prints in particular show good light and wet fastnesses and good chlorine fastnesses.

5

Example 2

86.5 parts of sulfanilic acid are dissolved in 500 parts of water at pH 4.5 with the addition of sodium hydroxide solution. Diazotization is then carried out as described in Example 1.

A filtered solution of 189.5 parts of l-acetylamino-8-io 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 pumped in at about 8 ° within one hour, the pH being kept at 6.5 with sodium carbonate solution. The dye that forms is largely precipitated. It is diluted to 3000 parts by volume by adding water and allowed to stir overnight at room temperature.

The dye suspension obtained is mixed with 500 parts of an I-molar copper sulfate solution and with 50 parts of sodium 20 um acetate. At 15 °, 90 parts of sodium perborate are first sprinkled in within 2 hours, then 40 parts of a 30% strength hydrogen peroxide solution are added dropwise within one hour. It is gradually warmed to 40 ° and stirred at 40 ° for 3 hours. The copper-containing dye turns 25

precipitated at room temperature with 500 parts of sodium chloride and 2500 parts of methanol and filtered off. The dye paste obtained is mixed with water with adjustment to 1000 parts by volume. The acetyl group is split off by hydrolysis for 4 hours at 60 ° with 50 parts of solid sodium hydroxide. For isolation, the pH is adjusted to 5, the dye is precipitated by sprinkling in 225 parts of sodium chloride and filtered at 40 °.

The dye paste is again mixed with water with adjustment to 1000 parts by volume. Then condensing in portions of about 50 parts of cyanuric chloride is condensed within about 5 hours at 0-5 °, the pH being kept at 5 with sodium carbonate solution.

A solution of 56.1 parts of l-amino-2-methylbenzene-4-sulfonic acid in 450 parts of water is added dropwise to the dye solution thus obtained at 60 ° within about 4 hours. The pH of the solution is kept at 5 with soda. The dye that forms gradually precipitates. The pH is adjusted to 6.5 and the dye is filtered off.

The pressed dye is dissolved at 50 ° in water with adjustment to 1500 parts by volume. The solution is clarified with the addition of a little activated carbon, then the dye is precipitated by adding 150 parts of sodium chloride, filtered and dried. The dye corresponds to the formula he dyes and prints natural and regenerated cellulose in the form of other salts can be isolated. With these dyes bluish purple tones. The dyeings and cellulose fibers obtained according to one of those known for prints have good light and wet fastness properties and good reactive dyeing processes from long or short chlorine fastnesses. fleet can be dyed or printed. Stains and

Analogously to Example 1 or 2, further compounds prints can be produced which have good light and wet fastness properties and good ones of the formula I for which R4 is hydrogen-chlorine fastness. For the dyes listed in the tables and the other variables in the following Tables 1 substances, the shade J and 2 are given in the last column J. The dyes produced in this way are indicated on cotton in 45; it corresponds to sodium salts as a function of the production and isolation conditions, but they can also be carried out by a = reddish violet usual measures in the form of the free acid or in b = bluish violet.

Table 1

Example No. Position Rj Hai R2 R3 J

S03 Naim (position)

Ring A

3rd

4th

H

Cl h

ch3

a

4th

4th

H

Cl h

-ch2ch2oh a

5

4th

H

Cl

-ch2ch2oh

-ch2ch2oh a

6

4th

h ci ch3

- <o>

a

7

4th

H

F

H

-cmva a

8th

4th

H

Cl h

--q a

SO "Well

7

643873

Table 1 (continued)

Example No. position

Ri

Shark r2

S03Na im

(Position)

Ring A

9

4th

H

Cl

H

10th

4th

H

Cl

CH

11

4th

H

F

H

12

5

H

Cl

H

13

5

H

Cl

H

14

5

H

Cl

H

15

5

H

Cl

H

16

5

H

F

H

17th

4th

SOjNa (6)

Cl

H

18th

4th

do.

Cl

H

19th

4th

do.

Cl

H

20th

4th

do.

Cl

-CI

21st

4th

do.

Cl

H

22

4th

do.

Cl

H

23

4th

do.

F

H

24th

4th

do.

Cl

CH

25th

6

Cl (4)

Cl

H

26

6

do.

Cl

H

27th

6

do.

Cl

H

28

6

do.

CI

H

29

6

do.

Cl

H

30th

6

do.

F

H

31

6

do.

Cl

H

32

6

do.

Cl

H

R,

-p-

CH "

S03 Well

-ch2ch2so3na -ch2ch2oh h

ch3

-ch2ch2oh

-Cj>

SO Na ch3

S03 Well

~ 0> ~ S03Na

"<©>

S03Na -0- S03Sa 30 Na d>

/

CH

SO ^ Na j

H

CHj H

-CH2CH2OH -CH2CH2S03Na a a b b b b b b b b b b b b b b b b

Table 2 R

Example No. Position R] Hai -S

S03Na im (position) \ R

Ring A 3

/CH.—CH, \

33 4 H Cl _NX 2 CH0

X £ H0— CH./

J. Z

34 3 H Cl do.

643 873

Table 2 (continued) R

Example No. Position R, Hai -N J

S03 Naim (position)

Ring A 3

/ CH - CH2 ^

35 6 Cl (4) Cl -N Ob

XCH2 -CH ^

36 4 S03Na (6) Cl do. b

37 4 H Cl do. a

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

Staining instructions A 20

2 parts of the dye from Example 1 or 2 are dissolved in 100 parts of warm water (about 40 °), to which 10 parts of urea have been added. 30 parts of a 10% sodium carbonate solution and 0.5 part of 1-nitrobenz-ol-3-sulfonic acid sodium are added. This solution is used to impregnate a cellulosic tissue so that it absorbs 75% of its dry weight of dye solution. After drying, the fabric is damp-dampened at 102 ° for 5 to 10 minutes, rinsed thereon and soaped at the boil for 15 minutes.

After drying you get a reddish or bluish-violet coloration of good light and wet fastness as well as chlorine fastness.

Dyeing Instructions B

2 parts of the dye from Example 1 or 2 are dissolved with 50 35 parts of water and 20 parts of urea 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 on 20 parts of cotton fabric, so that the liquor absorption of the fabric is 80% of its 40 dry weight. The padded fabric is first dried in between, then steamed at 103 ° for 10 minutes. The dyeing is rinsed, soaped at the boil, rinsed again and then dried. You get a reddish or bluish purple color with good fastness level. 45

Analog to the regulations A and B, dyeing can also be carried out using the dye from Example 16; in this case steam is applied at 105 ° for 2 minutes. A bluish violet color is obtained.

Printing instruction

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

25 parts of the dye from Example 1 or 2

100 parts of urea

440 parts of water

400 parts of a 4% sodium alginate thickener, 10 parts of 1-nitrobenzene-3-sulfonic acid sodium, and 25 parts of sodium bicarbonate printed by the customary method.

The printed textile is steamed for 4-8 minutes at 102-104 ° and then rinsed cold and warm. After the hot soap with subsequent rinsing and drying you get a reddish or bluish purple print with good light and wet fastness and chlorine fastness.

In an analogous manner, a printing paste can be produced with the dye of Example 16; in this case the printed textile is steamed at 100 ° for 2 minutes. The result is a bluish violet print.

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

C.

Claims (5)

643 873 PATENT CLAIMS 1.Compounds of Formula I, so3H wherein Ri hydrogen, sulfo or halogen (only in position 4), R2 hydrogen, (1-4C) alkyl or hydroxy- (2-4C) alkyl, R3 (1-4C) alkyl, hydroxy- (2-4C) alkyl, H03S - (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) Can carry alkoxy, mean or R2 and R3 together with the N atom to which they are attached form a 6-membered heterocyclic ring which may contain a further heteroatom, and R3 also stands for hydrogen if the substitution 4-sulfo next to R, in the meaning of hydrogen, is excluded for ring A, R4 is hydrogen or (1-4C) alkyl and shark are fluorine, chlorine or bromine, and their salts, with the restriction that a compound of the formula I which contains 2 sulfo groups in ring A in positions 4 and 6, in which R4 stand for hydrogen, shark for chlorine and -NR2R3 for p-sulfanilino, are excluded from the scope. 2. A process for the preparation of compounds of the formula I or mixtures thereof, characterized in that, on the one hand, a cyanuric halide with the amount equivalent to the reaction of a halogen atom, on the one hand, of a copper-containing monoazoamino compound of the formula II, OH NHR, which can be in the form of the free acid or as a salt, or a mixture thereof, on the other hand the amine component of the formula III IV which can be in the form of the free acid or as a salt, on the one hand with the diazonium compound of an amine of For-25 mei V 30th R, 35 couples, on the other hand condenses with a cyanuric halide in such a ratio that only 1 halogen atom reacts, a halogen atom 40 of the cyanuric halide against the amine of the formula III at any time HNR2R3 III II, 45 exchanged under condensation and tallied at any time during the individual process steps or as a final reaction with a copper-containing compound. 3rd 643873 Hydrogen is available, converted into the metal complex by oxidative coppering and a compound of the formula I thus obtained is optionally converted into the salt. 3. A process for the preparation of compounds of the form which can be in the form of the free acid or as a salt and mei I or mixtures thereof, characterized in that 'wherein R5 is hydrogen or (1-4C) alkoxy, or a irrespective of the order of addition, the coupling mixture in the event that R5 is (1-4C) alkoxy, tion component of formula IV, by dealkylating copper or in the event that R5 for 4. A process for the preparation of compounds of formula I or mixtures thereof, characterized in that the compound of formula VI, hnr2r3 III 60 or a mixture thereof, the reaction being independent of the order of addition of a compound of the formula II and III, and if appropriate converted into the salts. 5. Process for dyeing leather, characterized in that dyeing with a compound of formula I or a mixture thereof.