CH666298A5 - FIBER REACTIVE MONOAZO CONNECTIONS. - Google Patents

Description

DESCRIPTION The invention relates to fiber-reactive monoazo compounds with a heterocyclic reactive radical, to processes

50 of their manufacture and use as reactive dyes in dyeing and printing processes.

The invention relates to compounds of the formula I.

(SO-H)

3 p

N = N

(S ° 3H> q

3 NÎ ^ N ci F

666 298

4th

correspond and are present as free acid or in salt form, where p is 1 or 2,

q is 0 or 1 and the sum of p + q is 2 or 3, R 1 is hydrogen, Ci-4-alkyl, Ci-4-alkoxy or SCbHund R: hydrogen, halogen, Ci-4-alkyl, Ci-4- Mean alkoxy, -NHCOCi-4-alkyl or -NHCONHî,

W stands for -N-Bi-N-,

I I

R3 Ri

Bi represents a divalent bridge member or Bi together with both groups -N (R3) ~ to which it is attached forms a piperazine ring or together with one of the two groups -N (Rj) - the rest

N-C2_4A1kylen-

or £ 3 ^

(S03H) n where n is 0 or 1,

Rj, independently of one another, is hydrogen, Ci-4-alkyl or substituted Ci-4-alkyl,

R4 -OR5, NH2, an aliphatic, cycloaliphatic, aromatic or heterocyclic amine residue and R5 is hydrogen, Ci-6-alkyl, substituted Ci-6-alkyl or phenyl.

In the naphthalene diazo component, the sulfo groups preferably occupy the following positions:

(a) Azo group bound in position 1, p + q = 2:

the sulfo groups are in positions 3,6 or 4, 6;

(b) Azo group bound in position 1, p + q = 3:

the sulfo groups are in positions 3,6, 8;

(c) Azo group bound in position 2, p + q = 2:

the sulfo groups are in positions 1.5; 1.6; 3.6; 4.8; 5.7 or 6.8;

(ci) more preferably in positions 3.6; 4.8 or 6.8;

(d) Azo group bound in position 2, p + q = 3:

the sulfo groups are in positions 3,6,8 or 4,6, 8.

The diazo component is preferably derived from 2-aminoaphthalene containing sulfogrup pen, which contains the sulfo groups in the preferred positions according to (c) and more preferably according to (ci) or according to (d).

The sum of p + q = 3 is particularly preferred.

In the present specification, unless otherwise indicated, each alkyl or alkylene group may be linear or branched. In a hydroxy-substituted alkyl or alkylene group which is bonded to a nitrogen atom, the hydroxyl group is not on the Ci atom.

R 1 and R 2 as alkyl or alkoxy preferably contain 1 or 2 carbon atoms and are in particular methyl or methoxy.

R2 as halogen preferably means chlorine or bromine, in particular chlorine.

R2 as -NHC0Ci-4-alkyl particularly preferably represents acetylamino.

Ri preferably means Ria as hydrogen, methyl,

Methoxy or SO3H; more preferably Rib as hydrogen or methoxy; Ri particularly preferably denotes hydrogen.

R2 preferably denotes R2a as hydrogen, chlorine, methyl, methoxy, -NHCOCH3 or -NHCONH2; more preferably Rib as hydrogen, methyl, -NHCOCH3 or -NHCONH2; particularly preferably R2c as -NHCOCH3 or 5-NHCONH2,

R3 as an alkyl preferably contains 1 or 2 carbon atoms. As substituted alkyl it is preferably C1-3 alkyl and preferably contains a substituent from the series hydroxy, chlorine, cyano, SO3H, OSO3H and COOH, of which particularly preferred is hydroxy.

R3 preferably represents R3a, where R3a, independently of one another,

Hydrogen, methyl, ethyl, -CH2CH2OH,

- (CH2) i-2 SOsH, - (CH2) i-20S03H or 15 - (CH2) i-3COOH. Further preferred for R3b, where R3b independently of one another denotes hydrogen, methyl, ethyl or -CH2CH2OH. Even more preferred for Rjc, where R3c, independently of one another, denotes hydrogen, methyl or ethyl; R3 particularly preferably represents 20 hydrogen.

R5 as alkyl is preferably Ci-4-alkyl, in particular Ci-2-alkyl. Rs as substituted alkyl preferably contains up to four carbon atoms and is preferably monosubstituted by hydroxy, C1-2-alkoxy or carboxy.

25 Rs preferably denotes Rsa as hydrogen, Ci-4-alkyl,

C2-4-alkyl or carboxy-Ci-4-alkyl monosubstituted by hydroxy or Ci-2-alkoxy; more preferably Rsb as Ci-2-alkyl.

R4 as a substituted amino group preferably carries one or two groups from the series Ci-4-alkyl, Cs-6-cycloalkyl and phenyl, these groups being unsubstituted or being able to carry customary substituents; or it forms a saturated or unsaturated, optionally further substituted 5- or 6-membered heterocyclic ring which can include up to 35 two further heteroatoms, such as N, O or S, and can optionally be further substituted. If the amino group is disubstituted, the two groups can be the same or different.

A substituted alkyl group in the 40 amino group defined for R4 is preferably Ci-4-alkyl, which is substituted by one or two groups (more preferably by one group) from the series OH, Ci-4-alkoxy, chlorine, cyano, COOH, SO3H, OSO3H, hydroxy-C2-4-alkoxy, phenyl,

substituted phenyl, NH2, -NHCi-4-alkyl and -N (Ci-4-45 alkyl) 2 is substituted.

A substituted phenyl radical in the amino group defined for R4 preferably carries one to three groups from the series halogen (more preferably chlorine), Ci-4-alkyl, C1-4-alkoxy, SO3H and COOH.

50 A substituted cycloalkyl group in the amino group defined for R4 is preferably cyclohexyl which carries up to three Ci-4-alkyl groups.

A heterocyclic amino group defined as R4 is preferably a 6-membered saturated ring which can contain a further O-55 or N atom. If it is substituted, then preferably up to three Ci-4-alkyl groups, more preferably up to three methyl groups.

R4 preferably represents R4a as -ORsa or -NRôR?, Where Ró and R7, independently of one another, are hydrogen, 60 C1-4-alkyl; C 1 -C 4 -alkyl monosubstituted by hydroxy, Ci-4-alkoxy, COOH, SO3H, hydroxy-C2-4-alkoxy, NH2, -NHCi-4-alkyl or -N (Ci-4-alkyl); Cyclohexyl, cyclohexyl substituted with 1 to 3 methyl groups; Phenyl or phenyl-Ci-4-alkyl, in which the phenyl radical in each case is further unsubstituted or substituted by one or two groups from the halogen series, preferably chlorine, C1-4-alkyl

Ci-4-alkoxy, SO3H and COOH, or Re and R7

5

666298

together with the N atom to which they are attached form a or 5- or o-membered, saturated or unsaturated, heterocyclic ring which can include a further O or N atom and which, if it carries further substituents, up to can contain three methyl groups. R »is more preferably R.4b as -ORsb or -NR6aR7a, where Róa and R7a, independently of one another, are hydrogen, Ci-2-alkyl; Ci-3-alkyl monosubstituted by hydroxy, COOH, SO3H, hydroxy-C2-4-alkoxy or -N (Ci-2-alkyl); Phenyl or phenyl-Ci-2-alkyl, the phenyl radical of which is in each case further unsubstituted or substituted by one or two groups from the series chlorine, methyl, methoxy, SO3H and COOH, or Róa and R7a together with the N atom to which they are bound to form a piperidine, morpholine, piprazin or N-methylpiperazine ring. Even more preferably, R4 is R4c as -NRòbR7b, where Rób and R7b, independently of one another, are hydrogen or C2-3-alkyl monosubstituted by hydroxy or 2-hydroxyethoxy. R4 particularly preferably represents R4d as -NRócR7c, in which R «c and R7c, independently of one another, denote hydrogen or 2-hydroxyethyl.

A divalent bridging member as Bi is preferably a C2-6 alkylene chain which is optionally interrupted by one or two heteroatoms and / or can be substituted by 1 or 2 hydroxyl groups; a phenylene group or two phenylene groups which are linked to one another by a divalent bridge such as -O-, -NH-, N = N-, alkylene, hydroxyalkylene or triazinylamino, each phenylene group either being further unsubstituted or, independently of one another, being substituted by up to two groups from the series halogen, Ci-4-alkyl, Ci-4-alkoxy, SO3H and COOH; furthermore, the phenylene groups are preferably bonded in the 1,3- or 1,4-position.

The bridge member Bi preferably means Bi as a C2-6 alkylene chain which is optionally interrupted by -O- or -N- and is unsubstituted or monosubstituted by SO3H or COOH, Q in 3- or 4- or 3'- or 4'-position is bound and Q for -NH-, -O-, -N = N-,

C2-4 alkylene, hydroxy-C3-4alkylene or for the group

N -

I.

R,

10th

3t> "3b

R4x with R4x is chlorine or R4c;

15 further preferred Bib as C2-3-AlkyIen, C2-3-Alkylen-0-

C2-3 alkylene, monohydroxy-substituted C3-4 alkylene, optionally 1,3- or 1,4-phenylene monosubstituted by SO3H or as

20th

25 in which Qa is bound in the 3- or 4- or 3- 'or 4'-position and

Qa for -O-, C2-3 alkylene or

35

R-5 Ti I

3CN ^ N 3C Cl

R3b is;

even more preferably Bic can be monosubstituted by hydroxy as C2-3 alkylene, 2-hydroxypro; as mono- or 40-pylene or 1,3- or 1,4-phenylene; dihydroxy-substituted C3-6 alkylene; optionally by particularly preferred Bid as C2-3 alkylene or 2-Hy-SO3H or COOH monosubstituted phenylene or as one. droxypropylene.

group

45 W preferably means Wi as a bridge -N-Bia-N-,

I I

R3b Rjb in which each phenylene group, independently of one another, goes on like this

N-C2_3A1kylen-N- or -N N

\ (

wherein m is 0 or 1;

R3b

(SO-H)

/ —V

further preferred W2 as N-Bib-N-,

I I

Rßc R3c

3 'm

3b even more preferably W3 as -N-Bic-N-;

I I

R3C R3C

/ \

or -N N-CH2CH2-N-;

r3c means particularly preferably

W W4 as -NH-Bid-NH-,

666298 6

Preferred compounds correspond to formula Ia

(S03H> p

N = N

(S03H> q o

1b

^ 0Y

3c "Y" R4b

2b n ~ K

W2 ~ \ 0 / N

Cl F

la and are present as free acid or in salt form,

wherein the sulfo groups of the naphthyl radical are arranged in the positions according to (ci) or (d), as described above.

Further preferred are compounds of the formula Ia in which (1) Rib is hydrogen and R2b is R2c;

(2) R3c is hydrogen;

(3) R4b stands for R4c;

(4) R4b is R4d;

(5) Compounds of the formula Ia, in which the sum of p + q = 3 and the three sulfo groups are arranged in the positions according to (d);

(6) those of (1) to (5), wherein w2 is W3;

(7) those of (6), where w3 is W4.

The nature of the cation of the sulfo groups and any additionally present carboxy groups in compounds of the formula I, if these are in salt form, is not a critical factor, but can be any chemical reactive dye

15

20th

25th

30th

act usual non-chromophores cation. However, the prerequisite is that the corresponding salts meet the condition of 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, of which sodium is particularly preferred.

In general, the cations of the sulfo groups and optionally carboxy groups in a compound of formula I may be the same or different and represent a mixture of the above-mentioned cations, i.e. the compound may also be in a mixed salt form.

The present invention further comprises a process for the preparation of the compounds of the formula I, characterized in that a compound of the formula II,

(S03H) p (SO ^ H)

3 'q

"■" "0TIQÏ

W-H

Y

R,

II

which is present as a free acid or in salt form, is reacted with 5-chloro-2,4,6-trifluoropyrimidine.

This condensation is carried out according to a conventional method.

The compounds of the formula I can be isolated in a manner known per se; e.g. the compounds can be separated from the reaction mixture by conventional salting out with alkali metal salts, filtered off and dried in vacuo.

Depending on the reaction and isolation conditions, a compound of formula I is considered free

Acid or preferably in salt form or as a mixed salt and then contains, for example, one or more of the above cations. Salts or mixed salts can, however, also be prepared starting from the free acid in a manner which is customary per se and vice versa, or it is also possible to carry out a salination which is customary per se.

The starting compounds of formula II can be obtained by using a compound of formula III,

= N

(S03H) P (SOjH),

ì R. R2

III

7

666298

which is present as free acid or in salt form, reacted with cyanuric chloride in a molar ratio of 1: i, then introduces the remainder Rt by chlorine exchange and condenses in the last stage with the diamine H-W-H.

The individual condensation reactions are carried out in a manner known per se.

The compounds of the formula III and diamines of the formula H-W-H are either known or can be obtained analogously to methods known per se from known starting materials.

The compounds of the formula I according to the invention and mixtures thereof are reactive dyes; they are suitable for dyeing or printing hydroxyl- and nitrogen-containing, textile or non-textile organic substrates. The preferred substrates are leather and textile materials which consist of or contain natural or synthetic polyamides and in particular natural or regenerated cellulose, such as cotton, viscose or rayon wool. The most preferred substrate is textile material consisting of or containing cotton.

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. The optimal and therefore preferred temperature range is in the cold dyeing range, i.e. at temperatures of 30-60 ° C. Furthermore, the compounds of the formula I are particularly well suited for African printing, with cotton primed with Naphthol AS being used for printing.

The compounds according to the invention can, as individual dyes or, because of their good combinability, also as a combination element with other reactive dyes of the same class, which have comparable dyeing properties; e.g. regarding general fastness properties, pull-out value, etc., can be used. The combination dyeings obtained show good fastness properties as do the dyeings with individual dye.

Because of their high building capacity, the compounds of formula I have high pull-out and fixing values. The unfixed dye portion can be washed out easily. The dyeings and prints obtained and in particular those prints obtained in combination with Naphthol AS show particularly good light fastness; but they also have good wet fastness properties, e.g. with regard to fastness to washing, water, seawater and perspiration. A particular advantage of the present dyes is their good resistance to oxidative influences such as chlorine-containing water, hypochlorite bleach, peroxide bleach and detergents containing perborate.

The following examples serve to illustrate the invention. In the examples, parts mean parts by weight or parts by volume and percent, percentages by weight or volume; the temperatures are given in degrees Celsius.

example 1

19.15 parts of 2-aminonaphthalene-3,6,8-trisulfonic acid are stirred in 110 parts of water and dissolved with the addition of 6 parts of 30% sodium hydroxide solution. 18.5 parts of 30% hydrochloric acid are then added. After the addition of 100 parts of ice, the mixture is zotatized for 45 minutes with a solution of 3.5 parts of sodium nitrite in 10 parts of water at 0-5 °. The mixture is stirred for 45 minutes and then a solution of 8.3 parts of 3-aminophenylurea in 75 parts of water is poured in. The pH is adjusted to 4.5 with 9 parts of sodium bicarbonate and held at this value for 30 minutes until the coupling has ended. The 20 monoazoamino dye formed is salted out with 90 parts of sodium chloride, isolated and dried in vacuo at 80 °.

32.7 parts of the monoazoamino dye prepared above are dissolved at pH 6.0 in 600 parts of water at 20 °. The solution is poured into a suspension of 12.7 parts of Cya-25 nonchloride in 350 parts of ice water. The pH is kept at 6.0-6.5 by adding 22 parts of 20% sodium carbonate solution. After the condensation has ended, the reaction temperature is allowed to rise from 0-5 ° to room temperature, and at the same time the pH is raised to 12.0 with 12.5% strength aqueous ammonia solution. After 30 minutes, the reaction mixture is warmed to 40 °, the pH is allowed to drop to 9.0 and is held at this value for three hours until the end of the condensation by adding a further 12.5% ammonia solution. A total of 35 50 parts of 12.5% aqueous ammonia solution are required.

The pH of the reaction mixture is adjusted to 5.8 with 50 parts of 10% hydrochloric acid, then a solution of 9.2 parts of 1,2-propylenediamine, 80 parts of water 40 and 12 parts of 10% hydrochloric acid, which has a pH of 6 , 2 has poured. The mixture is heated to 86 ° within 60 minutes and held at this temperature for five hours. At the same time, a pH of 5.8-6.1 is maintained by adding 40 parts of 20% sodium carbonate solution. For isolation, the pH is adjusted to 3.2 with 20 parts of 10% hydrochloric acid. Salt out with 190 parts of sodium chloride and then filter. The dye is obtained according to the formula

21 parts of this dye are kept in 450 parts of water 6.5-7.0. The reaction is resolved after 6-7 hours. At pH 6.5-7.0 and room temperature, 8 parts of 65 are ended. The condensation product is added in portions by adding 5-chloro-2,4,6-trifluoropyrimidine, salting out 50 parts of sodium chloride, isolating by filtration, adding 44 parts of 20% sodium and drying at 50 ° in vacuo. The color carbonate solution of the pH obtained during the condensation in the case of the substance corresponds to the formula

666298

8th

s ° 3h so3h n «n

NH

so3h nhconh2

NH,

f nhchgchnh - / qn

CH, '^ 3 Cl F

It dyes cotton in golden yellow tones. The dyeings and prints on cotton obtained by conventional methods, especially in combination with Naphthol AS dyes, show good light and wet fastness properties and are independent of oxidative influences.

Examples 2-62

Analogously to the method described in Example 1, further compounds of the formula I can be prepared using appropriate starting materials. Formula (A) applies to these dyes,

d-n =

R

I.

B.j -N

3rd

M

Cl

(A)

whose symbols are listed in the following table.

The individual residues D have the following meaning:

Di = 3,6,8-trisulfonaphthyl-2 D: = 4,6,8-trisulfonaphthyl-2 Dì = 3,6,8-trisulfonaphthyl-1 Ü4 = 4,8-disulfonaphthyl-2 Ds = 6,8-disulfonaphthyl -2 Dó = 3,6-disulfonaphthyl-2 Dt = 1,5-disulfonaphthyl-2 Ds = 3,6-disulfonaphthyl-1 D? = 4,6-disulfonaphthyl-l

In the bridge Bi, the C atom marked with * is bound to the -N (R3) group, which connects the triazine ring.

With the compounds of Examples 2-62, substrates which consist of or contain cellulose, in particular cotton substrates, can be dyed or printed in yellow to golden yellow tones by customary drawing and printing processes. The dyeings and 35 prints on cotton obtained, in particular the prints obtained in combination with Naphthol AS, are good light and wet fast and resistant to oxidative influences.

With the dyes of Examples 2-5; 15-18; 22,26,27, 30-32,36,37,40-42; 47-49; 52-54; 57-59 and 62 yellow tones are obtained on 40 cotton; with the dyes of Examples 6-14; 19-21; 23-25; 28,29,33-35; 38,39,43-46; 50.51, 55.56, 60 and 61 are obtained golden yellow tones on cotton.

table

Example No. D

Ri

R2

R3

R4

Bi

Tue

Tue

H

H

NHCOCH3

NHCOCHÎ

H

H

-NH2

-NH2

scmcH-I

CH3 -CH2CHCH2-

Tue

Dl

H

H

NHCOCH3 H -NHCH2CH2OH

NHCOCH3 H -NHCH2CH2OH

OH

-CH2CHCH2-

I.

OH

* CH2CH-

6

7

Tue

Tue

H H

NHCONH2 H NHCONH2 H

-NHCH2CH2OH -NHCH2CH2OH

CHs

-CH2CH (OH) CH2-SCH2CH-

Tue

H

NHCONH2 H

-NH2

CH3 -CH2CHCH2-

OH

666298

Table (continued)

Example No. D Ri r2

R3

r4

Bi

9

Tue

H

10th

Tue

H

11

D2

H

12

D2

H

13

D2

H

14

D2

H

15

D2

H

16

D2

H

17th

D2

H

18th

Tue

H

19th

Tue

H

20th

D2

H

21st

D2

H

22

D2

H

23

24th

25th

26

27th

28

29

30th

Tue Tue

Tue there

Since d4

d4

d4

OCHs OCH3

OCHs ch3

NHCONH2 NHCONH2 NHCONH2

NHCONH2 NHCONH2

NHCONH2 NHCOCH3

NHCOCH3

ch3

ch3

ch3

ch3

och3 H och3 ch3 och3 ch3

H H H

H H

H H

-N (CH2CH20H) 2 -CH2CH2-

-NHCH2CH2OCH2CH2OH -CH2CH2 - NH2 ± CHîCH-

NHCOCH3 H NHCOCH3 H NHCOCH3 CHs

NHCONH2 H NHCONH2 H NHCONH2 H

H

H H

H H

H

H

H

H

NHCOCH3 H

-NH2

-NHCH2CH2OH

-NHCH2CH2OH -NHCH2CH2OH

-NHCH2CH2OH

-NH2

-NH2

-NH2 -NH2 -NH2

-NHCH2COOH

-NH2 -NH2

-NHCH2CH2OH -NHCHa

-NH2 -NH2

-NHCH2CH2SO3H -NCH2CH2SO3H

I.

CH3

CH3 -CH2CHCH2-

I.

OH -CH2CHCH2-

I.

OH

CH3 ÌCH2CH-

I.

CH3

-CH2CH (OH) CH2 - CH2CH (OH) CH2 - CH2CH (OH) CH2-

X7

O

-O

-CH2CH (OH) CH2-ÏCH2CH-

I.

CH3

-CH2CH (OH) CH2- * CH2CH-

I.

CH3

-O-

CH2CH2 ^ Q-

* CH2CH-

I.

CH3 iCH2CH-

I.

CHs * CH2CH-

I.

CH3

31

d4

H

nhcoch3

H

-NCH2CH2SO3H

I.

CH3

17th

S0oH

666298

Table (continued)

Example No. D Ri R2

10th

ra r4 bi

32

33

34

35

04

Ds

Ds

Ds

H

H

NHCOCH3 H

OCH3 CH3

OCHs CH3

H

H

NHCONH2 H

-NHCH2CH2OH

-NHCH2CH2OH

-NHCH2CH2OH

-NHCH2CH2OH

^ 0-

so3h

SCH2CH-

I.

CH3 -CH2CHCH2-

I.

Oh

-CH2CHCH2-

I.

Oh

36

37

38

39

40

41

Ds Ds Ds

Do

Dó Dò

H H

H H

OCH3 CHs

OCH3 CHs

H

C2H5 H

H

H CH3 H

SOsH NHCOCH3 H

-N (CH2CH20H) 2 -N (CH2CH20H) 2 -NH2

-NH2

-NH2 -NH2

-CH2CH2 - CH2CH2-SCH2CH-

I.

CH3 SCH2CH-

I.

CH3

-CH2CH20CH2CH2 -CH2CH2-

42

43

44

Do

DÖ Dé

H

H

OCHs CH3 OCHs CH3

CH3

H H

-NH2

-NH2

-NHCH2CH2OH

-oiws-o-

Y

Cl

-CH2CH (OH) CH2-SCH2CH-

I.

CHs

45

46

Do

D?

h h

NHCONH2 H

NHCONH2 h so3h

-OC2H5

-CH2CH2-

s0, h h-

47

48

DT

D7

H NHCOCH3 H

OCHs H H

cooh

-nh-ö-s ° 3h

-NH (ch2) 3n (ch3) 2

* ch2ch-I

CH3 * CH2CH-

i

CHs

49

Ds

H

NHCOCH3 H

-N (CH2CH20H) 2

-O-0-O-

11 666298

Table (continued)

Example No.D Ri R: R3 R4 Bi

50

That is

51

9

H

52

D9

H

53

Tue

54

Tue

OCHs nhconh2 nhconh2 NHCOCH3 H

H

H

CH3 h

C2H5

H

-N (CH2CH20H) 2

-nh2

-OH

-NH (CH2) 3N (CH3) 2

-NH (CH2) 3N (C2H5) 2

-ch2ch2och2ch2-

-ch2ch (oh) ch2-

-ch2ch (oh) ch2-

* ch2ch-I

CH3 ïch2ch-

I.

CH3

55

di

H

nhconh2 H

-nh2

56

57

58

59

60

61

62

d2

d2

d5

DO

d2

d2

Tue

H

H

SO3H

H

OCH3 OCH3

nhconh2 NHCÒCH3 NHCOCH3

NHCOCH3

CH3 CH3

OCH3 H

H H H

h h h h

-nhch2ch2och2ch2oh -ch2ch2 - nh2

-NHCH3

-NHCH2CH2SO3H

-nh2

-nhch2ch2oh

-nhch2ch2cooh

-O-

"Q-

SO ^ H

s ° 3h

-CH2CH (OH) CH2-iCH: CH-

I.

CH3 îCH2CH-

I.

CHs

Examples 63-65

Analogously to the method described in Example 1, further compounds of the formula I can be prepared using the corresponding starting compounds of the following formula

= NH

n ^ n nh2

w n so3h r2

correspond; for example 63 it means R2 = -nhconh2;

Cl

(B)

w = - n n - \ - J

Color on cotton: golden yellow

666298

12

for example 64

R: = -NHCONH2

W = - n n-ch2ch2nh-

Color on cotton: golden yellow for example 65 W = - n n-chochpnh- color on cotton:

R2 = -NHCOCH3; \ -! yellow

(The N atom marked with * is bound to the triazine ring light and wet fastness and good resistance.) Against oxidative influences.

According to the method described above, the dyes of Examples 1 to 65 are obtained as sodium salts. Depending on the reaction and isolation conditions chosen or by subsequent measures, they can be prepared in a manner known per se in the form of the free acid or in another salt form or else mixed salt form and then, for example, one or more of the cations listed further in the description contain.

Possible uses of the compounds according to the invention are illustrated below.

Example of use A (pull-out method)

In a dyebath containing 0.3 part of the dye from Example 1 or 44 and 15 parts of Glauber's salt (calcined) in 300 parts of demineralized water, 10 parts of cotton yarn (bleached) are introduced at 40 °. After 30 minutes at 40 °, a total of 6 parts of soda (calcined) are added at intervals of 10 minutes, in portions of 0.2; 0.6; 1,2 and finally 4 parts, keeping the temperature at 40 °. The dyeing is then continued at 40 ° for one hour.

The dyed material is then rinsed in running cold water for 3 minutes, then in running hot water for 3 minutes. The color is soaped for 15 minutes in 500 parts of demineralized water and 0.25 part of sodium lauryl sulfonate. After rinsing in running water (hot for 3 minutes), centrifugation is carried out and the color is dried in a drying cabinet at approx. 70 °. A gold-yellow cotton dyeing of good is obtained in each case

Example of use B (print)

A printing paste with the components 40 parts of the dye from Example 1.6 or 7 100 parts of urea 20 340 parts of water

500 parts of a 4% sodium alginate thickening 20 parts of soda 1000 parts in total

25 is applied to cotton material by the usual printing processes.

The printed material is dried and then fixed with steam at 105 ° for one minute. The fixed cotton material is then rinsed hot, soaped at the boil (analogous to the method described in application example A) and dried. The gold-yellow print obtained in each case has good general fastness properties and is resistant to oxidative influences.

Example of use C (Naphtol AS printing)

A printing paste prepared from the components according to application example B is applied to cotton cretonne (leached), which was colored before printing with Naphtol AS. The printing is carried out according to printing processes known per se. The cotton prints obtained in this way have remarkably good lightfastness properties.

In an analogous manner to that in application examples A to C, dyeing or printing can also be carried out with the dyes of the other examples or with mixtures of the dyes from examples 1-65.

35

40

B

Claims (8)

666 298 1. Compounds corresponding to formula I 2nd PATENT CLAIMS fl, N "( ■■ -p-n'Ôî '"" « ) - R „N ^ N Cl F R Y R, (S0, H) 3 P (S ° 3H) correspond to q and are present as free acid or in salt form, where p is 1 or 2, q is 0 or 1 and the sum of p + q is 2 or 3, R 1 is hydrogen, Ci-4-alkyl, Ci-4-alkoxy or SO3H and Rs hydrogen, halogen, Ci-4-alkyl, Ci-4-alkoxy , -NHCOCi-4-alkyl or -NHCONH2 mean, W stands for -N-Bi-N-, I I R3 Rj Bi stands for a divalent bridge member or Bi together with both groups -N (Rj) - to which it is attached, a piperazine ring or together with one of the two groups -N (Rj) - the rest -N ^) - C2-4alkylene- or-Ii ^ »J - \ ^ f <S03H>, v forms where n is 0 or 1; R3, independently of one another, is hydrogen, Ci-4-alkyl or substituted Ci ^ t-alkyl, R4 -OR5, NH2, an aliphatic, cycloaliphatic, aromatic or heterocyclic amine radical and R5 is hydrogen, Ci-6-alkyl, substituted Ci-ö-alkyl or phenyl. 2. Compounds according to claim 1, wherein Ri represents Ria as hydrogen, methyl, methoxy or SO3H and R2 represents R2a as hydrogen, chlorine, methyl, methoxy, -NHCOCH3 or -NHCONH :. 15 Meaning of -N-Bia-N-, I I R3b R3b 20 -N N-, 25 or N-C2_3Alky1en-N - R3b 30 where m is 0 or 1, Bia a C2-6 alkylene chain which may be replaced by-0- or -N- I. Rjb is interrupted and may be further substituted by monohydroxy; monohydroxy or dihydroxy substituted C3-6 alkylene; Phenylene or phenylene monosubstituted by SO3H or COOH; 3 Q 3 ' or a group 40 means in which the phenylene radicals are each, independently of one another, further unsubstituted or monosubstituted by SO3H or COOH, Q is bonded in positions 3 or 4 or 3 'or 4' and Q is -NH-, -O-, -N = N-, C2-4 50 alkylene, hydroxy-C3-4 alkylene or the group 3. Compounds according to claim 1, wherein R4 is R4b meaning -ORsb or -NRóaR? A, Rsb Ci-2-alkyl and Rfia and R7a, independently of one another, hydrogen, C1-2-55 alkyl; C1-3 — alkyl monosubstituted by OH, COOH, SO3H, hydroxy-C2-4-alkoxy or -N (Ci-2-alkyl); Phenyl or phenyl-Ci-2-alkyl, the phenyl of which is unsubstituted or further substituted by one or two groups from the series consisting of chlorine, methyl, methoxy, SO3H and COOH, or 60 Rèa and R? A together with the N atom, to which they are attached form a piperidine, morpholine, piperazine or N-methylpiperazine ring. 4. Compounds according to claim 1, wherein W stands for Wi 65 in the :, JI T R 3b N ^ N R4x 3b stands in which R4 * denotes chlorine or R4c, R4c for -NRshRib, Rób and R7b, independently of one another, for hydrogen or C2-3-alkyl monosubstituted by hydroxy or 2-hydroxyethoxy, and R3b, independently of one another, for hydrogen, methyl, Ethyl or 2-hydroxyethyl are available. 5. Compounds according to claim 1, which of the formula Ia 3rd 666298 (S03H> p N = N (S03H) q 4b correspond to la and exist as free acid or in salt form, in which the sulfo groups in the naphthyl radical are in the 3,6-, 4,8- or 6,8-position in the case that the sum of p + q2 and in the case that the sum of p + q is 3, in 3, 6, 8- or 4-, 6-, 8-position, Rib for hydrogen or methoxy and R2b for hydrogen, methyl, -NHCOCH3 or -NHCONH2 stand, R4b is as defined in claim 3, W2 for -N-Blb-N-, ^ 3c ^ 3c / —V -N N- 6. Compounds according to claim 5, wherein Rib is hydrogen, R2b is R2cals -NHCOCH3 or -NHCONH2 and Rio 15 are each hydrogen. 7. Compounds according to claim 5, wherein R4b is R4d has the meaning of the radical -NR6cR7c, wherein Ree and R7c, independently of one another, are hydrogen or 2-hydroxyethyl. 20 8. Compounds according to claim 5, wherein W2 is W4 as -NH-Bid-NH- and Bia means C2-3 alkylene or 2-hydroxypropylene. 9. A process for the preparation of compounds of the formula I, defined in claim 1, characterized in that a compound of the formula II, defined as free acid, Ri or -N ^ ^ N-CI ^ C ^ N-, ^ 3c Rjc, independently of one another, for hydrogen, methyl or ethyl, and Bib for C2-3-alkylene, C2-3-alkylene-0-C2-3-alkylene, monohydroxy-substituted C3-4-alkylene; 1,3- or 1,4-phenylene, 1,3-or 1,4-phenylene monosubstituted by SO3H; or for the group 30th 35 (SO-H) 3 'p N = N (S0, H) W-H II stand in which Qu is bound in positions 3 or 4 or 3 'or 4 and ~ N N Qu -O-, C2-3-alkylene or the radical R0 “11 3c n ^ N 3c means. Cl wherein R 1, R 3, R 4, W, p and q are as defined in claim 1, with 5-chloro-2,4,6-trifluoropyrimidine. 40 10. A method for dyeing or printing hydroxyl-containing or nitrogen-containing, non-textile organic substrates, characterized in that dyeing or printing with a compound of formula I, defined in claim 1, or with mixtures thereof. 45