GB2172896A

GB2172896A - Reactive formazan dye mixtures

Info

Publication number: GB2172896A
Application number: GB08606059A
Authority: GB
Inventors: Jurg Steiger
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1985-03-16
Filing date: 1986-03-12
Publication date: 1986-10-01
Also published as: FR2578852B1; GB8606059D0; IT1203749B; IT8647762A0; GB2172896B; CH667278A5; FR2578852A1; JPS61213267A

Abstract

Novel dye mixtures of two different formazans of formula I are useful for dyeing or printing leather or textiles of natural or synthetic polyamides or natural or regenerated cellulose, especially exhaust dyeing of cotton. <IMAGE> wherein m is 0, 1, 2 or 3; each R is halo, alkyl, alkoxy, SO3H, CO2H or NHCO alkyl; and R1 and R2 are each H or specified substituents or NR1R2 is a 5- or 6-membered saturated ring optionally with further hetero atoms or alkyl substituents.

Description

SPECIFICATION Improvements in or relating to organic compounds This invention relates to mixtures of formazan compounds containing a monochiorotriazinyl group, a process for their preparation and processes for dyeing or printing using these compound mixtures as fibre-reactive dyes.

According to the invention there is provided a compound mixture consisting of a compound (A) and a compound (B), characterised in that compounds (A) and (B) which are in free acid or salt form, correspond to formula I (one of the possible tautomeric forms),

in which the sulpho group is in the 4-or 5-position, R1 is hydrogen, C1 4alkyl, C14alkyI monosubstituted by halogen or cyano, or C2.4hydroxyalkyl, and R2 is hydrogen, C 4alkyl, Cos 6alkyl substituted by one or two groups selected from halogen, hydroxy, cyano, COOH, SO3H, OSO3H and OR4; phenyl or phenyl substituted by one or two groups selected from C1.4aIkyl, halogen, COOH, OR4 and -SO2R5, or R1 and R2, together with the N-atom to which they are attached, form a 5-or 6-membered saturated ring which contains one to three hetero atoms and is further unsubstituted or substituted by one to three C1.4alkyl groups, R4 isC1.4aikyl or C2 4hydroxyalkyl, Rs is hydroxy, amino, C14alkyl or phenyl, m isO,1,20r3,and each R is independently halogen, C1.4alkyl, C1 4alkoxy, SO3H, COOH or -NHCOC 4alkyl, provided that (i) compound (A) is different from compound (B);; (ii) when compound (A) is a compound of formula I, in which the sulpho group is in the 5-position, m isO, R1 is hydrogen and R2 is 4-sulphophenylamino, compound (B) is other than a compound of formula I, in which m, Ra and the position of the sulpho group are as defined for compound (A) and R2 is 3-sulphophenylamino.

Preferred are mixtures containing a compound (A) and a compound (B) in a ratio (by weight) of from 9:1 to 1:9; more preferably of from 4:1 to 1:4; most preferred are mixtures containing (A):(B) in a ratio of from 4:1 to 1:1, especially ca. 1:1.

Preferably, compound (A) differs from compound (B) with respect to the position of the sulpho group (4 or 5) and/or with respect to the -NR1R2 group bound to the chlorotriazinyl group. Most preferably, the sulpho group is in the 5-position on both compounds (A) and (B).

Generally, by halogen is meant fluorine, chlorine or bromine, preferably chlorine or bromine, most preferably chlorine.

Any alkyl or alkoxy group may be linear or branched unless indicated otherwise. In any hydroxy- or alkoxy-substituted alkyl group which is attached to a nitrogen atom, the hydroxy or alkoxy group is bound to a carbon atom other than to the C1-atom.

The phenyl group which may be substituted by m groups R is preferably unsubstituted (m = O), or it is substituted by one or two groups R, which may be the same or different. More preferably, this phenyl group is unsubstituted or substituted by one or two groups Ra, where each Ra is independently chlorine, Claalkyl, Cl,alkoxy, SO3H or -NHCOCH3. Even more preferably,this phenyl group is unsubstituted or substituted by one or two groups Rb, where each Rb is independently chlorine, methyl, methoxy or SO3H. Most preferably, the phenyl group is unsubstituted.

R4 is preferably R4a, where R4a is methyl, ethyl or 2-hydroxyethyl; more preferably R4 is 2-hydroxyethyl.

R5 is preferably R5a, where R5a is hydroxy, amino, methyl or ethyl. More preferably R5 is R5b is hydroxy or amino; most preferably R5 is hydroxy.

R1 is preferably Ria, where Ria is hydrogen, methyl, ethyl, Cm 3alkyl monosubstituted by chlorine or cyano, or C2.3hydroxyalkyl, or Ria, together with R2 and the nitrogen atom to which they are attached, forms 9 pyrrolidine, piperidine, morpholine, piperazine or N-methylpiperazine ring. More preferably, R1 is Rib, where Rib is hydrogen, methyl, ethyl or 2-hydroxyethyl, or Rib, together with R2 and the nitrogen atom to which they are attached, forms a morpholine, piperazine or N-methylpiperazine ring. Most preferably R1 is hydrogen.

R2 is preferably R2a, where R2a is hydrogen, methyl, ethyl, Alkyl monosubstituted by chlorine, cyano, COOH, SO3H or OSO3H; C2.4alkyI substituted by one ortwo hydroxy groups or by OR4a; phenyl or phenyl substituted by one or two groups selected from chlorine, methyl and -S02R5a; or R2a, together with R1 and the nitrogen atom to which they are attached, forms a pyrrolidine, piperidine, morpholine, piperazine or N-methylpiperazine ring.More preferably, R2 is R2b, where R2b is hydrogen, C1.3alkyl mono-substituted by COOH, SO3H or OSO3H; C2 3alkyl substituted by one ortwo hydroxy groups or by OR4a; phenyl or phenyl substituted by one or two groups selected from chlorine, methyl and -SO2R5b; or R2b, together with R1 and the nitrogen atom to which they are attached, forms a morpholine, piperazine or N-methylpiperazine ring.

Most preferably, R2 is R2c, where R2e is hydrogen or phenyl which is substituted by methyl and/or sulpho.

Preferred compounds correspond in one of the possible tautomericforms to formula la,

in which ma is 0, 1 or 2.

More preferred are compounds offormula la in which (1) Rib is hydrogen; (2) R2b is R2C; (3) Rib is hydrogen and R2b is R2C; (4) those of (1) to (3), in which m1 is 0; (5) those of (1) to (4), in which the sulpho group is in the 5-position.

Preferred mbcturns of compounds (A) and (B) are those, in which compound (A) is a compound of formula I, wherein R, is hydrogen and R2 is hydrogen or C2 4alkyl which is monosubstituted by hydroxy or OR4; and compound (B) is any compound of formula I, more preferably of formula la, different from compound (A) and which compounds (A) and (B) are present in a ratio (by weight) of from 4:1 to 1:4; more preferred mixtures are those, in which compound (A) is a compound of formula I, wherein Ra and R2 are both hydrogen; and compound (B) is any compound of formula I, more preferably of formula la, and most preferably of formula la, in which R2b is phenyl substituted by methyl and/or sulpho, different from compound (A), and which compounds (A) and (B) are present in a ratio (byweight) (A):(B) of from 4:1 to 1:1; most preferred mixtures are those, in which compound (A) is a compound of formula I, wherein R1 and R2 are both hydrogen, m is 0 and the sulpho group is in the 5-position; and compound (B) is any compound of formula la different from compound (A), in which the sulpho group is in the 5-position, m1 or 0, Rib is hydrogen and R2b is phenyl substituted by methyl and/or sulpho, and which compounds (A) and (B) are present in a ratio (by weight) (A):(B) of from 4:1 to 1:1, especially ca 1:1.

When in a mixture the compounds of formula I are in the salt form, the cation of the sulpho groups and any carboxy groups is not critical and may be any one of those non-chromophoric cations conventional in the field of reactive dyestuffs provided that the corresponding salts as obtained are water-soluble. Examples of such cations are alkali metal cations and unsubstituted or substituted ammonium cations, e.g., lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetra-methylammonium, triethylammonium, mono-; diand tri-ethanolammonium.

The preferred cations are the alkali metal cations and ammonium, with sodium being the most preferred.

In a compound of formula I the cations of the sulpho and carboxy groups can be the same or different, e.g., they can also be a mixture of the above mentioned cations meaning that the compound of formula I can be in a mixed salt form.

The present invention further provides a process for the preparation of mixtures of a compound (A) with a compound (B) comprising reacting one or more compounds which in one of the possible tautomericforms correspond to formula II

with one or more compounds of formula lil,

in which X is chlorine or - NR1 R2, where in the case when X is chlorine further reacting with one or more compounds of formula IV HNR1R2 IV is necessary, provided that at least two different starting compounds of the compounds of formulae II, Ill and/or IV are used.

The individual condensation steps on the triazine ring may be effected in accordance with conventional methods.

The mixtures of compounds of formula I may be isolated in accordance with known methods, for example, by conventional salting out with alkali metal salt, filtering and drying optionally in vacuo. Depending on the reaction and isolation conditions a mixture of compounds of formula I is obtained in free acid or preferably salt form or even mixed salt form containing, for example, one or more of the above mentioned cations. It may be converted from free acid form to a salt form or mixture of salt forms or vice versa or from one salt form to another by conventional means.

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

The starting compounds of formula II are either known or may be prepared in accordance with known methods using appropriate starting materiais.

The amines of formula IV are similarly either known or may be prepared analogously to conventional methods.

The mixtures of compounds of formula I are useful as fibre reactive dyestuffs for dyeing or printing hydroxy group or nitrogen containing organic substrates. The preferred substrates are leather and fibre materials containing or consisting of natural or synthetic polyamides and, particularly, of natural or regenerated cellulose such as cotton, viscose and spun rayon. The most preferred substrate is textile material containing or consisting of cotton.

Dyeing or printing is effected in accordance with known methods. However, for the mixtures of compounds of formula lit is preferred to use the exhaust dyeing method. An advantage is that dyeing with these dyestuffs is not temperature dependent in the usual dyeing temperature range. Therefore, dyeing may be effected almost equally well at 80"C as at 10000 without any essential loss of fixation yield.

The compound mixtures according to the invention are well compatible with other reactive dyes; they may be applied per se or in combination with appropriate fibre reactive dyestuffs of the same class having analogous dyeing properties e.g., extent of ability to exhaust from the dyebath onto the fibre, common fastness properties with respect to the resulting dyeings etc. The dyeings obtained with such combination mixtures have good fastness properties.

In view of their notable build-up power the mixtures of compounds of formula I give high exhaust and fixation yields. The portion of unfixed dyestuff can be easily washed off the substrate. The dyeings obtained show good light fastness and wet fastness properties such as wash, water, sea water and sweat fastness.

They are stable to any oxidative influences e.g., chlorinated water, hypochlorite bleach and peroxide or perborate containing wash liquors.

The following examples further serve to illustrate the invention. In the examples all parts and percentages are by weight or volume. The temperatures are in degrees Centigrade.

Example 1 19 parts of cyanuric chloride are added to a solution containing 60 parts of a compound of the formula

and 0.5 parts of a commercial wetting agent in 300 parts of water and 300 parts of ice. The pH of the solution is kept at 5-6 with a 15% soda solution until the end of acylation. Subsequently, 10 parts of 1-aminobenzene-3-sulphonic acid are added. The resulting suspension is heated to 50 and the pH is kept at 7-8 by adding a 15% soda solution. After three hours, 15 parts of a 25% ammonia solution are added. The reaction mixture is then stirred at 50 for a further time until the primary acylation product is no longer detectable.The dyestuff mixture thus formed, having the formula

in a ratio of ca. 1:1 (by weight) is salted out with a mixture of sodium chloride and potassium chloride, filtered off and dried. A dark blue dye powder is obtained which dyes cotton a clear blue shade. The cotton dyeings have good light and wet fastness properties and are remarkably stable to any oxidative influences.

Examples 2 to 22 By analogy with the method described in Example 1, using appropriate starting compounds, further mixtures of compounds of formula I may be prepared which are listed in the following Table. For these mixtures containing a compound (A) and a compound (B) in a ratio (by weight) of ca. 1:1 which compounds differ with respect to the position of the sulpho group or with respect to the -NRiR2 group bound to the triazine ring as defined in the Table, R is hydrogen. These mixtures disclosed in Examples 2 to 22 may be applied to cellulose fibres to the conventional exhaust dyeing method. The dyeings obtained have a blue shade; they show good light fastness and wet fastness properties and good stability to any oxidative influences.

TABLE - NR, R2 in -NR1R2in -NRiR2in Ex. No. position SO3H compound (A) compound (B)

2 5 -NH2 CH3 -NH SO3H 3 4 do. do.

3 4 do.

4 5 do. NHe S03H -NHCH2CH2OH do.

5 5 SO3H 6 4 -NH2 -NH do.

7 5 -NHCH2CH2OH do.

8 5 -NHCH2CH(OH)CH3 do.

9 5 -NHCH2CH2OCH2CH2OH do.

10 5 NH2 S03H -NH -Ij CH3 OjH 11 5 -NH2 SO3H -NH C1 12 4/5 -NHe S03H same as for compound (A) 13 4/5 -NH do.

S03H 14 4/5 -NHCH2CH2OCH2CH2OH do.

15 4/5 -NHCH2CH2SO3H do.

16 4/5 -N NH do.

17 4/5 -NH2 do.

18 5 do. -NHCH2CH2OH 19 5 do. -NHCH2CH(OH)CH2OH 20 5 do. -NHCH2CH(OH)CH3 21 5 do. NHCH2CH2SO3H 22 5 do. -NHCH2CH2OCH2CH2OH If by a method analogous to that described in Example 1 the quantities of amines used are changed, corresponding dyestuff mixtures are obtained containing the compounds (A) and (B) in a ratio (by weight) of ca. 3:1 to 1:3.

In accordance with the method as described the dyestuff mixtures of Examples 1 to 22 are obtained in the mixed sodium/potassium salt form. They may, depending on the reaction and isolation conditions or by reacting the mixed salts in accordance with known methods, also be obtained in free acid form or in other salt forms, for example those salt forms containing one or more cations indicated in the description above.

In the following examples the application of the dyestuff mixtures of this invention is illustrated.

Application Example A To a dyebath consisting of 1000 parts water, 20 parts Glauber's salt (calcined), 2.5 parts sodium carbonate (calcined) and 1 part of the sodium salt of 1-nitrobenzene-3-sulphonic acid are added 50 parts of mercerized cotton fabric. The bath is heated to 40 , then 2.5 parts of the dye mixture of Example 1 is added. The temperature is raised to 98" within 45 minutes; during this time 20 parts Glauber's salt (calcined) are added after 15 minutes and again 20 parts Glauber's salt (calcined) are added after further 15 minutes. At the end of this time 7.5 parts sodium carbonate (calcined) are added. Dyeing is continued at the boil for 45 to 60 minutes. Subsequently, the dyed fabric is rinsed hot and soaped at the boil for 20 minutes in 500 parts water and 0.5 parts sodium laurylsulphonate.After rinsing and drying a blue cotton dyeing with good light fastness and wet fastness properties is obtained.

Application Example B 0.5 Parts of the dyestuff mixture of Example 1 are dissolved in 300 parts water. 10 Parts cotton fabric are added and the temperature of the dyebath is raised to 800 within 10 minutes. 15 Parts Glauber's salt (calcined) are added and 30 minutes thereafter, 3 parts sodium carbonate (calcined). Dyeing is continued for one hour at 80". Subsequently, the dyed fabric is rinsed cold, then hot, and is soaped according to the method given for Application Example A. After rinsing and drying a blue cotton dyeing is obtained having good fastness properties.

Similarly, the dyestuff mixtures of Examples 2 to 22 may be employed to dye cotton in accordance with the method given for Application Examples A or B, whereby blue dyeings having good fastness properties are obtained.

Claims

1. A compound mixture consisting of a compound (A) and a compound (B), characterised in that compounds (A) and (B) which are in free acid or salt form, correspond to formula I (one of the possible tautomeric forms),

in which the sulpho group is in the 4-or 5-position, Ra is hydrogen, C1 4alkyl, C1.4alkyl monosubstituted by halogen or cyano, or C24hydroxyalkyl, and R2 is hydrogen, Cr4alkyl, C1 6al kyi substituted by one or two groups selected from halogen, hydroxy, cyano, COOH, SO3H, OSO3H and OR4; phenyl or phenyl substituted by one or two groups selected from Cl,alkyl, halogen, COOH, OR4 and -SO2R5, or R1 and R2, together with the N-atom to which they are attached, form a 5- or 6-membered saturated ring which contains one to three hetero atoms and is further unsubstituted or substituted by one to three C14alkyl groups, R4 is Calkyl, orC24hydroxyalkyl, R5 is hydroxy, amino, Alkyl or phenyl, m is0,1,2Or3,and each R is independently halogen, Ca4alkyl, C C14alkoxy, SO3H, COOH or -NHCOCi4alkyl, provided that (i) compound (A) is different from compound (B);; (ii) when compound (A) is a compound of formula I, in which the sulpho group is in the 5-position, m is O, R1 is hydrogen and R2 is 4-sulphophenylamino, compound (B) is other than a compound of formula I, in which m, Ra and the position of the sulpho group are as defined for compound (A) and R2 is 3-suiphophenylamino.

2. A mixture according to Claim 1, for which in formula I R1 is Ria, where Ria is hydrogen, methyl, ethyl, C1.3alkyl monosubstituted by chlorine or cyano, or C2 3hydroxyalkyl, or Ria, together with R2 and the nitrogen atom to which they are attached, forms a pyrrolidine, piperidine, morpholine, piperazine or Nmethylpiperazine ring.

3. A mixture according to Claim 1 or 2, for which in formula I R2 is R2a, where R2a is hydrogen, methyl, ethyl, C1 4alkyl monosubstituted by chlorine, cyano, COOH, SO3H or OSO3H;C2.4alkyI substituted by one or two hydroxy groups or by OR4a; phenyl or phenyl substituted by one or two groups selected from chlorine, methyl and -SO2R5a; or R2a, together with R1 and the nitrogen atom to which they are attached, forms a pyrrolidine, piperidine, morpholine, piperazine or N-methylpiperazine ring, R4a is methyl, ethyl or 2-hydroxyethyl, and R5a is hydroxy, amino, methyl or ethyl.

4. A mixture according to any one of Claims 1 to 3, for which in formula I m is 0,1 or 2 and R is Ra, where each Ra is independently chlorine, C1 2alkyl, C1 2alkoxy, SO3H or -NHCOCH3.

5. A mixture according to Claim 1, for which the compounds of formula I correspond to formula la,

in which the sulpho group is in the 4- or 5-position, m1 isO, 1 or 2, each Rb is independently chlorine, methyl, methoxy or SO3H, Rlb is hydrogen, methyl, ethyl or 2-hydroxyethyl, or Rib, together with R2 and the nitrogen atom to which they are attached, forms a morpholine, piperazine or N-methylpiperazine ring, and R2b is hydrogen, C1.3alkyl monosubstituted by COOH, SO3H or OSO3H; CzBalkyl substituted by one or two hydroxy groups or by OR4a; phenyl or phenyl substituted by one or two groups selected from chlorine, methyl and -SO2R5b; or R2b, together with R1 and the nitrogen atom to which they are attached, forms a morpholine, piperazine or N-methylpiperazine ring.

R4a is methyl, ethyl or 2-hydroxyethyl, and R5b is hydroxy or amino.

6. A mixture according to Claim 5, for which in formula la Rlb is hydrogen and R2b is R2CI where R2C is hydrogen or phenyl which is substituted by methyl and/or sulpho.

7. A mixture according to Claim 5 or 6, for which in formula lam1 isO.

8. A mixture according to any one of the preceding claims, in which compound (A) differs from compound (B) with respect to the -NR1R2 group bound to the chlorotriazinyl group.

9. A mixture according to any one of the preceding claims, in which on both compounds (A) and (B) the sulpho group is in the 5-position.

10. A mixture according to any one of Claims 1 to 9, containing the compounds (A) and (B) in a ratio (by weight) of from 9:1 to 1:9.

11. A mixture according to Claim 10, in which the ratio (A):(B) is from 4:1 to 1:4.

12. A mixture according to Claim 1 or 11, in which compound (A) is a compound of formula I, wherein R, is hydrogen and R2 is hydrogen or C2 4alkyl monosubstituted by OH or OR4; and compound (B) is any compound of formula I, different from compound (A), which compounds (A) and (B) are present in a ratio (by weight) of from 4:1 to 1:4.

13. A mixture according to Claim 5 or 12, in which compound (B) is any compound of formula la, defined in Claim 5, different from compound (A).

14. A mixture according to Claim 1, in which compound (A) is a compound of formula I, wherein R, and R2 are both hydrogen; and compound (B) is any compound of formula I, different from compound (A), which compounds (A) and (B) are present in a ratio (by weight) (A):(B)offrom 4:1 to 1:1.

15. A mixture according to Claim 5 or 14, in which compound (B) is any compound of formula la, defined in Claim 5, different from compound (A).

16. A mixture according to Claim 15, for which in a compound of formula la R2b is phenyl substituted by methyl and/or sulpho.

17. A mixture according to Claim 1 or 5, in which compound (A) is a compound offormula I, wherein Ra and R2 are both hydrogen, m is 0 and the sulpho group is in the 5-position; and compound (B) is any compound of formula la, defined in Claim 5, different from compound (A), in which the sulpho group is in the 5-position, m1 is 0, Rib is hydrogen and R2b is phenyl substituted by methyl and/or sulpho, which compounds (A) and (B) are present in a ratio (by weight) (A):(B) of from 4:1 to 1:1.

18. A mixture according to Claim 17, in which the ratio (A):(B) is ca. 1:1.

19. A compound mixture defined in Claim 1, substantially as herein described with reference to any one of Examples 1 to 22.

20. A process for the peparation of mixtures of a compound (A) with a compound (B), defined in Claim 1, comprising reacting one or more compounds which in one of the possible tautomeric forms correspond to formula II

in which R, m and the position of the sulpho group are as defined in Claim 1, with one or more compounds of formula Ill,

in which Xis chlorine or -NR1R2, where in the case when Xis chlorine further reacting with one or more compounds of formula IV HNR,R2 IV in which R and R2 are as defined in Claim 1, is necessary, provided that at least two different starting compounds of the compounds of formulae 11, Ill and/or IV are used.

21. A process for the preparation of a compound mixture, defined in Claim 1, substantially as herein described with reference to any one of Examples 1 to 22.

22. A compound mixture, defined in Claim 1, whenever obtained by a process according to Claim 20 or 21.

23. A process for dyeing or printing hydroxy group or nitrogen containing organic substrates comprising applying a compound mixture according to any one of Claims 1 to 19 or 22 as dyeing or printing agent.

24. A process according to Claim 23, wherein said substrate is leather or a textile containing or consisting of natural or regenerated cellulose.

25. A process according to Claim 24, wherein said substrate is a textile containing or consisting of cotton.

26. Dyed or printed substrates whenever obtained by a process according to any one of Claims 23 to 25.