CH667278A5 - REACTIVE FORMAZAN CONNECTIONS. - Google Patents

Description

DESCRIPTION The compound relates to mixtures of formazan compounds which contain a monochlorotriazinyl group, processes for the preparation and processes for dyeing or printing non-textile organic substrates using these compound mixtures as reactive dyes. The invention accordingly relates to compound mixtures which consist of a compound (A) and a compound (B), characterized in that the compounds (A) and (B), which are present as free acid or salt form, in one of the possible tautomeric forms of formula I.

SO.H

CQOH

Correspond to <R> m, in which the sulfo group is in position 4 or 5,

Ri for hydrogen, Q ^ alkyl, C ^ alkyl or C2 ^ hydroxylalkyl monosubstituted by halogen or cyano and

R2 represents hydrogen, C1-4 alkyl, C1-4 alkyl substituted by one or two substituents from the series halogen, hydroxy, cyano, COOH, SOîH, OSO3H and OR4; Phenyl or phenyl substituted by one or two groups from the series C ^ alkyl, halogen, COOH, OR4 and -SO2R5 or

Ri and R2 together with the N atom to which they are attached form a 5- or 6-membered saturated ring,

which includes one to three heteroatoms and which can be substituted by one to three C ^ alkyl groups,

R4 for C ^ alkyl or C2_4hydroxyalkyl,

Rs for hydroxy, amino, Ci ^ alkyl or phenyl,

m for 0,1,2 or 3 and

R, independently of one another, represent halogen, Ci ^ alkyl, Ci ^ alkoxy, SO3H, COOH or -NHCOC ^ alkyl, with the proviso that

(i) Compound (A) is different from Compound (B);

(ii) if compound (A) is a compound of formula I in which the sulfo group is in position 5, m is 0, Ri is hydrogen and R2 is 4-sulfophenyl, compound (B) has a different meaning than that of one A compound of formula I wherein m, Ri and the position of the sulfo group are as defined for compound (A) and R2 is 3-sulfophenyl.

Mixtures which contain a compound (A) and a compound (B) in a weight ratio of 9: 1 to 1: 9, more preferably 4: 1 to 1: 4, are preferred. Mixtures which contain (A) :( B) in a weight ratio of 4: 1 to 1: 1, in particular of about 1: 1, are particularly preferred.

Compound (A) preferably differs from compound (B) with regard to the position of the sulfo group (in position 4 or 5) and / or with regard to the group -NR1R2 bonded to the monochlorotriazinyl ring. The sulfo group is particularly preferably in the 5-position for both compounds (A) and (B).

Halogen generally represents fluorine, chlorine or bromine, preferably chlorine or bromine, in particular chlorine.

Each alkyl or alkoxy group, unless otherwise stated, can be straight or branched. A hydroxyl or alkoxyalkyl group bound to a nitrogen scheme contains the hydroxyl or alkoxy group in a different position than at the Ci atom; a dihydroxyalkyl group does not carry the two hydroxide groups on the same carbon atom.

The phenyl radical optionally substituted by m groups R is preferably unsubstituted (m = 0), or it carries one or two substituents R, which may be the same or different. This phenyl ring is furthermore preferably unsubstituted or bears one or two substituents Ra which, independently of one another, represent chlorine, Ci_2alkyl, C 1-4 alkoxy, sulfo or -NHCOCH3; the phenyl radical is even more preferably unsubstituted or carries one or two substituents Rb which, independently of one another, are chlorine, methyl, methoxy or sulfo. The phenyl ring is particularly preferably unsubstituted.

R4 preferably represents R (a as methyl, ethyl or 2-hydroxyethyl; more preferably R4 stands for 2-hydroxyethyl.

Rs preferably denotes R5a as hydroxy, amino, methyl or ethyl; more preferably R5b as hydroxy or amino; in particular Rs stands for hydroxy.

Ri preferably denotes R) a as hydrogen, methyl, ethyl, Ci_3alkyl or C2_3hydroxylalkyl monosubstituted by chlorine or cyano, or Rla pictures together with Rz and the N atom to which they are attached, a pyrrolidine, piperidine, morpholine, Piperazine or N-methylpiperazine ring; more preferably R [b as hydrogen, methyl, ethyl or 2-hydroxyethyl, or RIb forms together with R2 and the N atom to which they are attached a morpholine, piperazine or N-methylpiperazine ring; Ri particularly preferably denotes hydrogen.

R2 preferably represents R2a as hydrogen, methyl, ethyl, C 1 -C 6 alkyl monosubstituted by chlorine, cyano, COOH, SO3H or OSO3H; is substituted by one or two hydroxyl groups or by a group OR (a substituted C2 ^ alkyl; phenyl or by one or two groups from the series chlorine, methyl and -S02R5a; or R2a

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

667 278

4th

together with Ri and the N atom to which they are attached, a pyrrolidine, piperidine, morpholine, piperazine or N-methylpiperazine ring; further preferably for R2b as hydrogen, C 1 -C 4 alkyl monosubstituted by COOH, SO3H or OSO3H, by one or two hydroxyl groups or by C2_3alkyl substituted by a group OR4a; Phenyl or phenyl substituted by one or two chlorine, methyl, and -S02R5b groups; or R2b together with Ri and the N atom to which they are attached forms a morpholine, piperazine or N-methylpiperazine ring; particularly preferred for R2c as hydrogen or phenyl substituted by methyl and / or sulfo.

Preferred compounds correspond in one of the possible tautomeric forms to the formula Ia,

HO3S5

20th

Ia where mi is 0, 1 or 2.

Further preferred compounds of the formula Ia are those in which

(1) Ru represents hydrogen;

(2) R2b is R2c;

(3) R, b is hydrogen and R2b is R2c;

(4) those of (1) to (3), where mi is 0;

(5) those from (1) to (4) in which the sulfo group is in position 5.

Preferred mixtures of compounds (A) and (B) are those for which compound (A) is a compound of the formula I in which R 1 is hydrogen and R 2 is hydrogen or C 2 -C 4 alkyl monosubstituted by hydroxyl or OR 4; and Compound (B) is any compound of Formula I, more preferably Formula Ia, other than Compound (A) and for which Compounds (A) and (B) are in a weight ratio of 4: 1 to 1: 4 present; more preferred are mixtures for which compound (A) is a compound of formula I in which R 1 and R 2 are both hydrogen; and Compound (B) is any compound of Formula I, more preferably Formula Ia, and particularly Formula Ia, wherein R2b is methyl and / or sulfo substituted phenyl, which is different from Compound (A) and for which the compounds (A) and (B) are present in the weight ratio (A) :( B) = 4: 1 to 1: 1; mixtures are particularly preferred for which compound (A) is a compound of the formula I in which R 1 and R 2 are both hydrogen, m is 0 and the sulfo group is in the 5-position; and compound (B) represents any compound of formula Ia, other than compound (A), in which the sulfo group is in the 5-position, mi is 0, rib is hydrogen and R2b is phenyl substituted by methyl and / or sulfo, and for which the compounds (A) and (B) are present in the weight ratio (A) :( B) = 4: 1 to 1: 1, in particular approximately 1: 1.

If the compounds of the formula I are in salt form in a mixture, the nature of the cation represents the

65

Sulfo group and any additional car-boxy groups present are not a critical factor, but can be any non-chromophoric cation which is customary in the field of reactive dyes, provided the condition of water solubility is fulfilled for the corresponding salts.

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

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

The invention further comprises a process for the preparation of mixtures of a compound (A) with a compound (B), which is characterized in that one or more compounds which are in one of the possible tautomeric forms of the formula II

h03s

II

in which R, m and the position of the sulfo group 40 are as defined above, with one or more compounds of the formula III,

45

ClyNYC1

"Yn iii in which X is chlorine or -NR1R2, and in the case where X is chlorine, then one or more verso compounds of the formula IV,

HNR1R2

IV

wherein R 1 and R 2 are defined as above, with the proviso that at least two different starting compounds of the compounds of the formulas II, III and / or IV are used.

The individual condensation reactions on the triazine ring take place analogously to the method known per se.

The mixtures of the compounds of the formula I can be isolated in a manner known per se; for example, they can be separated from the reaction mixture by conventional salting out with the corresponding alkali metal salt or salt mixture, filtered off and dried (if appropriate in vacuo).

Depending on the reaction and isolation conditions, a mixture of the compounds of the formula I is in the form of the free acid or preferably in salt form or as

5

667 278

mixed salt obtained 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 a salting operation which is per se customary can also be carried out.

Furthermore, it is also possible to prepare the compound mixtures according to the invention by simply mixing the individual compounds (A) and (B), which are present as free acid or in salt form, in any desired weight ratio.

The starting compounds of the formula II are known or they can be obtained analogously to processes known per se using the corresponding starting materials.

The amines of the formula IV are also known or they can be prepared analogously to processes which are customary per se.

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

The compound mixtures can be used in dyes or in printing pastes by all dyeing and printing processes customary for reactive dyes. The pull-out method is preferably used. It is a particular advantage of these dyes that they can be used in a dyeing temperature range from 80 ° to 100 ° C. without a significant loss in color yield; at 80 ° C the color yield is usually almost as good as at 100 ° C.

The dye mixtures according to the invention can, as such or because of their good combinability, also be used as combination elements with other suitable reactive dyes of the same class which have comparable dyeing properties, for example with regard to the ability to extract, fastness properties of the dyeings obtained, etc. The resulting combination dyeings show good fastness properties.

Because of their high build-up capacity, the mixtures according to the invention of the compound of the formula I have high extraction and fixing values; the unfixed dye is easily washable. The dyeings obtained have a good fastness level, in particular with regard to light and general wet fastness properties such as fastness to washing, water, sea water and sweat. They are also resistant to oxidative influences such as chlorine-containing water, hypochlorite bleach, peroxide bleach or detergents containing perborate.

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

example 1

To a solution of 60 parts of the compound of the formula

NH "

ÄXÄ

SO, H N N ^ so H

* I II U

and 0.5 part of a commercial wetting agent in 300 parts of water and 300 parts of ice, 19 parts of cyanuric chloride i5 are added. The pH is kept at 5-6 with 15% sodium carbonate solution until the end of the acylation. Then 10 parts of l-aminobenzene-3-sulfonic acid are added. The suspension is heated to 50 ° and the pH is kept at 7-8 by adding 15% sodium carbonate solution. After three hours 20 15 parts of 25% ammonia solution are added, then the reaction mixture is stirred at 50 ° until the primary acylation product is no longer detectable. The dye mixture formed according to the formula

N- <C1

NHRo

S0, H N u

3 I II S03H

with Rg = H

and R

--TS

2 \ /

S03H

in a weight ratio of approx. 1: 1

J

45

is salted out with a mixture of sodium chloride and potassium chloride, filtered off and dried. The dark blue dye powder obtained dyes cotton in clear blue tones. The dyeings are light and wet fast, so they have a remarkable stability against oxidative influences.

Examples 2 to 22

Analogously to the method described in Example 1, 55 further mixtures of compounds of the formula I can be obtained using appropriate starting compounds, which are summarized in the following table. These mixtures contain the compound (A) and the compound (B) in a weight ratio of about 1: 1, whereby for the individual mixtures the compounds (A) and (B) each differ with regard to the position of the sulfo group or with respect to the distinguish the triazine ring-bound group -NR1R2, as defined in the table, and R represents hydrogen. The mixtures disclosed in Examples 2 to 22 can be used for cellulose fibers in accordance with the customary pull-out method; dyeings in blue tones are obtained. The dyeings are light and wet fast and show good stability against oxidative influences.

667 278

6

table

Example No.

Position of

-NR1R2 in

-NRIR2 in

s03h

Connection (A)

Connection (B)

ch,

\ 0

2nd

5

-nh2

-nh- ^ r \ -s03h

3rd

4th

do.

do.

4th

5

do.

-nh- ^ y ~ s03h

5

5

-nhch2ch2oh do.

so, h

/ 3rd

6

4th

-nh2

7

5

-nhch2ch2oh do.

8th

5

-nhch2ch (0h) ch3

do.

9

5

-nhch2ch20ch2ch20h do.

s03h

10th

5

-nh2

-M-0 ch3

; ° 3h

11

5

-nh2

- nh—

Cl

12

4/5

_nh ^ ySo3h as in connection (A)

13

4/5

so3h do.

14

4/5

-nhch2ch2och2ch2oh do.

15

4/5

-nhch2ch2so3h do.

16

4/5

/ - \ —n nh do.

7

667 278

Example No.

Position of the S03H

-NR ^ R2 in connection (A)

-NRIR2 in connection (B)

17th

4/5

-NH2

do.

18th

5

do.

-NHCH2CH2OH

19th

5

do.

-NHCH2CH (0H) CH20H

20th

5

do.

. -NHCH2CH (OH) CH3

21st

5

do.

-nhch2ch2so3h

22

5

do.

-NHCH2CH20CH2CH20H

If, in analogy to Example 1, amine amounts are used in changed ratios, corresponding dye mixtures are obtained which contain the compound (A): compound (B) in a ratio of about 3: 1 to 1: 3.

According to the method described above, the dye mixtures of Examples 1 to 22 are obtained as a mixed sodium / potassium salt. 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 dye mixtures according to the invention are illustrated below.

Staining instructions A

50 parts of mercerized cotton are added to a color tape consisting of 1000 parts of water, 20 parts of Glauber's salt (calcined), 2.5 parts of soda (calcined) and 1 part of 1-nitrobenzene-3-sulfonic acid sodium. The bath is heated to 40 °, then 2.5 parts of the dye mixture from Example 1 are added. The bath is heated to 98 ° within 45 minutes; 20 parts of Glauber's salt (calcined) are added twice every 15 minutes. At the end of

7.5 parts of soda (calcined) are then added for 45 minutes. Subsequently, the dyeing is continued for 45 to 60 minutes, then rinsed hot and the dyed material is soaped at the boil for 20 minutes in 500 parts of water and 0.5 part of sodium lauryl sulfonate. After thorough 3o rinsing and drying, you get a good light and wet fast cotton dyeing with a blue tint.

Dyeing Instructions B

0.5 part of the dye mixture from Example 1 is dissolved in 35 300 parts of water. 10 parts of cotton fabric are added to the dyebath, the temperature is set to 80 ° within 10 minutes. 30 minutes after the addition of 15 parts of Glauber's salt (calcined), 3 parts of soda (calcined) are added to the dyebath. The dyeing is continued at 80 ° for 40 hours. The dyed material is then cold first, then rinsed hot and soaped in the same way as for regulation A. After rinsing and drying, a blue color is obtained with good fastness properties.

45 In an analogous manner to that described in Regulations A and B, the dye mixtures of Examples 2 to 22 can also be used for dyeing cotton, blue dyeings with good fastness properties likewise being obtained.

Claims (10)

667 278 1 * 2 in which the sulfo group is in position 4 or 5, Ri for hydrogen, C ^ alkyl, C ^ alkyl or C2 ^ hydroxyalkyl monosubstituted by halogen or cyano and R2 represents hydrogen, C1-4 alkyl, Ci ^ alkyl substituted by one or two substituents from the series halogen, hydroxy, cyano, COOH, SO3H, OSO3H and OR4; Phenyl or phenyl substituted by one or two groups from the series C ^ alkyl, halogen, COOH, OR4 and -SO2R5 or R 1 and R 2 together with the N atom to which they are attached form a 5- or o-membered saturated ring which includes one to three heteroatoms and which can be substituted by one to three C 1 -C 6 alkyl groups, R4 for Ci ^ alkyl or C2 ^ | hydroxyalkyl, R5 for hydroxy, amino, C 1-4 alkyl or phenyl, m for 0, 1, 2 or 3 and R, independently of one another, are halogen, C ^ alkyl, Ci ^ jalkoxy, SO3H, COOH or -NHCOCi ^ alkyl, with the proviso that (i) Compound (A) is different from Compound (B); (ii) if compound (A) is a compound of formula I in which the sulfo group is in position 5, m is 0, Ri is hydrogen and R2 is 4-sulfophenyl, compound (B) has a different meaning than that of one A compound of formula I wherein m, Ri and the position of the sulfo group are as defined for compound (A) and R2 is 3-sulfophenyl. 2. Mixture of compounds according to claim 1, for which the compound of formula I of formula Ia Cl N- < m - ((> .4CXÀ1 T ï S »v ? Rib R2b 25th 30th 35 Ia, where the sulfo group is in position 4 or 5, mi is 0.1 or 2, each Rb, independently of one another, chlorine, methyl, methoxy or SO3H, Rlb is hydrogen, methyl, ethyl or 2-hydroxyethyl, or Rlb together with R2b and the N atom to which they are attached forms a morpholine, piperazine or N-methylpiperazine ring, and R2b is hydrogen, Ci_3AJkyl monosubstituted by COOH, SO3H or OSO3H; C2_3alkyl substituted by one or two hydroxy groups or by OR ^; Phenyl or phenyl substituted by one or two groups from the series chlorine, methyl and -S02R5b, or R2b together with Rlb and the N atom to which they are attached forms a morpholine, piperazine or N-methylpiperazine ring , Rta for methyl, ethyl or 2-hydroxyethyl, and R5a represent hydroxy or amino. 2nd 1. A mixture of compounds consisting of a compound (A) and a compound (B), characterized in that the compounds (A) and (B), which are present as free acid or in salt form, in one of the possible tautomeric forms of the formula I. J1 , N- ( 'V A N NN ^ S0_H II 3 3rd 667 278 in which R, m and the position of the sulfo group are as defined in claim 1, with one or more compounds of the formula III, C1 ^ N ^ C1 X in which X represents chlorine or -NR1R2, and in the event that X represents chlorine, then one or more compounds of the formula IV, HNR1R2 ™ wherein Ri and R2 are as defined in claim 1, with the proviso that at least two different starting compounds of the compounds of formulas II, III and / or IV are used. 3. compound mixture according to claim 1 or 2, for which in both compounds (A) and (B) the sulfo group is in position 5. 4. A compound mixture according to one of claims 1 to 3, which contains the compounds (A) and (B) in the weight ratio (A) :( B) = 4: 1 to 1: 4. 5. A mixture of compounds according to claims 1 to 4, for which compound (A) represents a compound of the formula I in which R 1 is hydrogen and R 2 is hydrogen or C 1 -C 4 alkyl monosubstituted by OH or OR 4; and compound (B) is any compound of formula I other than compound (A), compounds (A) and (B) being in a weight ratio of 4: 1 and 1: 4. 6. A compound mixture according to claim 1, in which compound (A) is a compound of formula I, wherein R 1 and R 2 both represent hydrogen; and compound (B) represents any compound of formula I other than compound (A), and compounds (A) and (B) are present in the weight ratio (A) :( B) = 4: 1 to 1: 1. 7. A compound mixture according to claim 1 or 2, for which compound (A) is a compound of formula I, wherein R 1 and R 2 are hydrogen, m is 0 and the sulfo group is in position 5; and compound (B) is any compound of formula Ia other than compound (A) defined in claim 2, wherein the sulfo group is in position 5, mi for 0, RIb for hydrogen and R2b for by methyl and / or Are sulfo substituted phenyl, and the compounds (A) and (B) in the weight ratio (A) :( B) = 4: 1 to 1: 1 are present. 8. A compound mixture according to claim 7, for which the weight ratio (A) :( B) is approximately 1: 1. 9. A process for the preparation of mixtures of a compound (A) with a compound (B) according to claim 1, characterized in that one or more compounds which are in one of the possible tautomeric forms of the formula II 55 H03s 60 65 II 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 mixture according to claim 1.