GB2108142A - Metal complex azo compounds - Google Patents

Abstract

Mixtures of symmetrical and asymmetrical 1:2 cobalt complexes of compounds of the formulae <IMAGE> wherein, each R1, independently, is hydrogen or C1-4alkyl, each R2, independently, is hydrogen, halogen, C1-4alkyl, C1-4alkoxy, or cyano, each R3, independently, is hydrogen, halogen, C1-4alkyl or C1-4alkoxy, and each X, independently, is OH or NH2, which complexes are optionally in salt form and which mixtures are useful for dyeing or printing substrates dyeable with anionic dyes, e.g., natural and synthetic polyamides such as wool, silk and nylon, polyurethanes, polyolefins modified to contain basic groups, leather and metals such as anodically oxidized aluminum.

Description

SPECIFICATION Improvements in or relating to organic compounds The present invention relates to mixtures of metal complex azo compounds, their preparation and use as anionic dyestuffs.

More particularly, the present invention provides a mixture of symmetrical and asymmetrical 1:2 cobalt complexes of the azo compounds of formulae I and 11,

in which compounds each Rr, independently, is hydrogen or C,~4alkyl, each R2, independently, is hydrogen, halogen, C,~4alkyl, C,~4alkoxy or cyano, each R3, independently, is hydrogen, halogen, C,~4alkyl or C,~4alkoxy, and each X, independently, is OH or NH2, which complexes are in free acid or salt form with respect to the cation neutralizing the negative charge of the complex anion of each 1:2 cobalt complex as well as to the carboxy group of the compound of formula II.

Preferably, the complex mixture contains the compounds of formulae I and 11 in a molar ratio range of from 80:20 to 20:80, more preferably 70:30 to 30:70, even more preferably 60:40 to 40:60, with a ratio of 1:1 being most preferred.

Any alkyl as R1, R2 and/or R3 may be straight chain or branched and is preferably methyl or ethyl, with methyl being most preferred.

Any alkoxy as R2 and/or R3 is preferably methoxy or ethoxy, with methoxy being most preferred.

By halogen is meant fluorine, chlorine or bromine. The preferred halogen is chlorine.

Each P1 is preferably R" where RI, independently, is hydrogen or methyl. More preferably, each R, is hydrogen.

Each R2 is preferably R2, where P2,, independently, is hydrogen, cyano, chlorine, methyl, methoxy or ethoxy. More preferably, R2 is R2', where R2', in dependently, is hydrogen, chlorine, methyl or methoxy.

Most preferably, each R2 is hydrogen.

Each R2 is preferably P3,, where P3,, independently, is hydrogen, chlorine, methyl, methoxy or ethoxy. More preferably, each R3 is R3', where R3', independently, has one of the significances of R2'.

Most preferably, each R3 is hydrogen.

Preferably, the phenyl group of the coupling component is unsubstituted.

Where an R2/R3 bearing phenyl ring is monosubstituted, each substituent is preferably chlorine, cyano, methyl, methoxy or ethoxy. Where the phenyl ring is disubstituted, the substituents are preferably in the 2,4-, 2,5-, 2,6- or 3,4-positions, with the 2,5- and 2,6-positions being most preferred, whereby each R2 and R3 is most preferably chlorine, methyl or methoxy and the substituents R2 and R3 may be the same or different.

The groups X in the coupling components of the monoazo compounds of formulae I and II are preferably both OH or are both NH2, especially OH.

The carboxy group in the monoazo compound of formula II is preferably in the 2-position.

Preferred mixtures of complexes are those, in which, in the compounds of formulae I and 11, (1) the groups P1, independently, are RI; (2) the groups R2 and R3, independently, are R2 and R'3: (3) the groups R2 and R3, independently, are R2' and Rát; (4) those of (1 ) to (3), in which, in the compounds of formulae I and 11, the groups X are both OH;; (5) more preferred are complex mixtures based upon metal free components of formulae la and Ila,

in which the groups R,, R2,1 and R' are independent of one another and in which R2' and R3,, when other than hydrogen are in the 2,5- or 2,6-positions; the component of formula Ia is preferably in salt form; (6) those of (5), in which, in the component of formula la, the significances of R'1, R2' and R' are identical with those in the component of formula Ila; (7) those of (5) or (6), in which R2' and R > t are hydrogen; (8) those of (1) to (7), in which R, is hydrogen; (9) those of (1 ) to (8), in which the compounds of formulae I(la) and ll(lla) are in a molar ratio of 6:4 to 4:6, especially in a 1:1 molar ratio.

The present invention also provides a process for the production of a mixture of symmetrical and asymmetrical 1:2 cobalt complexes of the compounds of formulae I and II, comprising reacting a mixture of the compounds of formulae I and Il with a cobalt donating compound. The metallisation of the mixture of monoazo compounds of formulae I and II may be carried out in accordance with conventional methods. It is preferred that the molar ratio of the mixture of compounds I and 11 to cobalt donating compound is 2:1. Suitable cobalt donating compounds are cobalt(ll)-sulphate, -acetate, formate and -chloride. It is particularly preferred to employ the compounds of formulae I and ll in a 1:1 molar ratio.

The mixture of 1:2 cobalt complexes obtained may be isolated in accordance with known methods, for example, the product may be salted out with an alkali metal salt or a weak acid, filtered, washed with an alkali metal salt solution and dried. The product obtained contains symmetrical and asymmetrical complexes in a relationship dependent upon the ratio of the compound of formula I to that of the compound of formula Il employed.

Depending on the reaction and isolation conditions the mixture of 1:2 cobalt complexes which may be obtained may be in free acid or preferably in salt form regarding the cation by which the negative charge of the complex anion of each 1:2 cobalt complex is balanced as well as the carboxy group in a compound of formula 11. The complex anion-neutralizing cation is not critical and may be any non-chromophoric cation conventional in anionic dyestuffs. Examples of such cations are alkali metal cations and cations of the ammonium type including unsubstituted and substituted ammonium cations e.g., lithium, sodium, potassium, ammonium; mono-, di-, tri- and tetra-methylammonium, triethylammonium, mono-, di- and tri-ethanolammonium, mono-, di- and tri-isopropanolammonium.

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

Similarly, the carboxy group is preferably in salt form, the cation of which may be any one of those indicated above for the complex anion-neutralizing cation and may be the same or different therefrom.

Preferably, the cation of the carboxylic acid group and the complex anion-neutralizing cation are the same, most preferably they are both sodium.

The monoazo compounds of formulae I and II are known or may be prepared in analogy with known methods from available starting materials. Preferably, the mixture of compounds of formulae I and il is prepared directly by diazotizing a mixture of amines of formulae Ill and IV,

in the desired ratio and coupling the obtained diazonium mixture with a compound of formula V,

or a mixture thereof, under alkaline to weakly acid conditions.

The product obtained may be directly metallized.

The mixtures of 1:2 cobalt complexes according to the present invention are highly soluble in water and are useful for dyeing or printing organic nitrogen-containing substrates dyeable with anionic dyes. They are particularly useful for dyeing or printing textiles consisting of or comprising natural and synthetic polyamides such as wool, silk and nylon, and also for dyeing synthetic polyamides in the mass.

The complex mixtures may advantageously be used for carpet printing, especially synthetic polyamide carpets. They are also useful for cross wound bobbin dyeing (cheese dyeing).

Similarly, the dyestuffs of the present invention may be employed for dyeing polyurethanes, basicmodified polyolefins, leather and metals such as anodically oxidized aluminum.

Dyeing and printing may be carried out in accordance with known methods.

The mixtures according to the present invention may be employed for dyeing as such or may be made up into liquid or solid preparations. The preparation of stable liquid, for example, concentrated aqueous preparations, or solid preparations may be carried out in accordance with conventional methods.

Preferably water-soluble organic solvents, optionally mixed with water, are used for the liquid preparations which are in the form of stable concentrated stock solutions; conventional additives such as dissolving agents (e.g. urea) may be added thereto. The stock solutions may be diluted with water.

Such preparations may be made, for example, in accordance with the procedure described in British Patent No, 1,112,032 or in British Patent No. 1,301,723. Concentrated stable aqueous preparations which contain conventional additives may also be used.

Solid preparations which are in powder or granulate form with an average particle size of at least 20 y can be used, which preparations contain conventional additives such as standardizing agents.

Such solid preparations may be made, for example, in accordance with the procedure described in British Patent No. 1,370,845. The solid preparations are highly soluble in water.

Further, the complex mixtures of this invention may be made up into preparations which are dispersible in cold water. Such dispersions may be prepared, for example, by grinding the dyestuff mixture dry or wet in an aqueous dispersing medium in the presence of one or more conventional anionic dispersing agents and optionally in the presence of other conventional additives, optionally with subsequent spray-drying. The preparations so obtained are finely dispersed in water.

The dyestuff mixtures according to the invention give dyeings which have notable light-fastness, good wet-fastnesses (wash-, water-, sea-water-, acid and alkaline sweat- and milling-fastness), ironingfastness, fastness to solvents, wet and dry rubbing-fastness, fastness to chlorine, carbonization-fastness and fastness to decatizing. The dyestuffs are not adversely affected by electrolytes or chalk.

The complex mixtures of the present invention exhaust from a neutral bath and brilt-up well on polyamide fibres. They have generally good build-up power and build-up equally on natural and synthetic polyamides when dyed in the same bath. They are also well suited for dyeing in combination with other asymmetrical or symmetrical 1:2 metal complex dyestuffs. The dyeings obtained with such combinations exhibit notable light-fastness.

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

EXAMPLE 1 39.6 Parts of 2-amino-1-hydroxybenzene-4-sulphonic acid-N-phenylamide and 46.2 parts of 2amino-1 -hydroxybenzene-4-sulphonic acid-N-phenylamide-2'-carboxylic acid are dissolved at 65 in 700 parts water at pH 10 with the addition of 30% sodium hydroxide solution and are then mixed with 20.7 parts sodium nitrite. The solution cooled to 05 is added dropwise over a period of 1 hour to 11 5 parts of 30% hydrochloric acid and 80 parts of ice, the temperature being maintained at 05 by the addition of further ice.

52.2 Parts of 3-methyl-1 -phenyl-5-pyrazolone are stirred to a fine suspension in 200 parts water and 33 parts of 30% sodium hydroxide solution. To this coupling suspension the above obtained diazo suspension is added over a period of 1 hour while maintaining the pH at 9.0-9.5 by the addition of 30% sodium hydroxide solution. After 3 hours coupling is completed and the monoazo dyestuff mixture is filtered.

For metallisation the paste of the monoazo dyestuffs is stirred in 1 800 parts of water and adjusted to pH 10 by the addition of 30% sodium hydroxide solution. At a temperature of 5060 , a solution of 42.2 parts cobalt(ll)sulphate in 120 parts water is added dropwise thereto over a period of 30 minutes, the pH being maintained at 10 by the addition of further sodium hydroxide. After metallisation the 1:2 cobalt complex mixture is salted out with sodium chloride, isolated by filtering, dried and ground. The dyestuff mixture obtained in the form of the sodium salt contains the two monoazo dyes of compounds lb and llb of the general formula

in which for lb R4 is H and for llb R4 is COONa in a 1:1 molar ratio.The mixture contains two symmetrical 1:2 cobalt complexes (a 1:2 complex of Ib/llb and a 1:2 complex of llb/llb) and an asymmetrical 1:2 cobalt complex of the compounds lb and llb.

The dyestuff mixture is highly soluble in water and dyes natural and synthetic polyamide fibres in reddish-yellow shades. The dyeings have good wet- and notable light-fastnesses.

In accordance with the procedure described in Example 1, further 1:2 cobalt complex mixtures may be prepared which contain monoazo dyes having the diazo components of compounds lb and llb of Example 1 and both having the same coupling component of formula V,

in a 1:1 molar ratio. The significances of X, R2 and R3 and the positions of the substituents in the phenyl ring are given in the following Table. The symbol I in the last column of the Table denotes the dye shade on natural or synthetic polyamide fibres, where a is reddish-yellow and b is reddish-brown.

The polyamide dyeings obtained have good light- and wet-fastnesses.

TABLE

Example No. X R2 (position) R3 (position) 2 OH Cl (2') H a 3 do. Cl (3') H a 4 do. Cl (4') H a 5 do. Cl (2') GI (5') a 6 NH2 H H b 7 do. Cl (2') H b 8 do. Cl (3') H b 9 do. Cl (4') H b 10 do. Cl (2') Cl (5') b 11 OH CN(3') H a 12 do. CH3 (2') H a 13 do. O2Hs(2') H a 14 do. OCH3(2') H a 15 do. OO2H5(4') H a 16 do. CH3 (3') H a 17 do. CH3 (4') H a 18 do. CH3 (2' ) CH3 (5') a 19 do. 0OH3(2') CH3 (5') a 20 NH2 CN(3') H b 21 do. CH3 (2' ) H b 22 do. CH3 (3') H b 23 do. CH3 (4') H b 24 OH ON (4' ) H a 25 do. cl (3') Cl (4') a 26 do. CH3 (2' ) Cl (6') a 27 NH2 Br (4') H b 28 do. CH3 (2' ) cl (6') b 29 do. Cl (3') Cl (4') b 30 OH CH3 (2' ) CH3 (6') a In analogous manner to the procedure described in Example 1 , further 1:2 cobalt complex mixtures containing the two monoazo dyestuffs of formulae lb and llb of Examples 1 to 30 in ratios of 30:70, 70:30, 40:60 and 60:40 may be prepared. The thus obtained dyestuff mixtures are also watersoluble and give dyeings on natural or synthetic polyamide fibres of reddish-yellow or reddish-brown shades. The dyeings have good light- and wet-fastnesses.

Further 1:2 cobalt complex mixtures may be prepared in analogy with the procedure described in Example 1 using monoazo compounds of formulae I and II containing non-identical coupling components and/or differing in the R,'s of the diazo components.

The complex mixtures of Example 1 and of Examples 2 to 30 of the Table which are in the sodium salt form may, depending on the reaction/isolation conditions, be obtained in accordance with known methods in free acid form or in other salt forms, for example those salt forms indicated in the description hereinbefore.

APPLICATION EXAMPLE A 1 Part of the 1:2 cobalt complex mixture of Example 1 is dissolved in 3000 parts water and 2 parts ammonium sulphate are added thereto. Subsequently, pre-wetted material (50 parts wool gaberdine or 50 parts nylon satin) is entered into a dyebath which is heated over a period of 30 minutes to boiling temperature. The material is dyed for a further 30 minutes, any evaporated water being replaced. Subsequently, the dyed material is rinsed and after drying, a reddish-yellow dyeing having notable light- and wet-fastnesses is obtained. The dyestuff mixtures of Examples 2 to 30 may be employed for dyeing in analogous manner.

APPLICATION EXAMPLE B Polyamide fabric is printed with a printing paste containing: 30 parts dyestuff complex mixture of Example 1, 50 parts urea, 50 parts dissolving agent (e.g. thiodiethylene glycol), 250 parts water, 500 parts thickening agent (e.g. based on carob bean gum), 60 parts acid-donating agent (e.g. ammonium tartrate), and 60 parts thiourea.

The printed textile goods are steamed for 40 minutes at 1020 (saturated steam), then rinsed with cold water, washed for 5 minutes at 600 with a dilute solution of conventional detergent and rinsed again with cold water. A reddish-yellow print having good light- and wet-fastnesses is obtained.

In analogous manner printing pastes may be prepared using any one of the dyestuff mixtures of Examples 2 to 30.

Claims (27)

1. A mixture of symmetrical and asymmetrical 1:2 cobalt complexes of the azo compounds of formulae I and II,

in which compounds each Fl1, independently, is hydrogen or C,~4alkyl, each R2, independently, is hydrogen, halogen, C,~4alkyl, C,~4alkoxy or cyano, each R3, independently, is hydrogen, halogen, C14alkyl or C,~4alkoxy, and each X, independently, is OH or NH2, which complexes are in free acid or salt form with respect to the cation neutralizing the negative charge of the complex anion of each 1:2 cobalt complex as well as to the carboxy group of the compound of formula li.

2. A mixture according to Claim 1, which comprises the compounds of formulae I and II in a molar ratio range of from 80:20 to 20:80.

3. A mixture according to Claim 2, wherein the molar ratio range is from 70:30 to 30:70.

4. A mixture according to Claim 3, wherein the molar ratio range is from 60:40 to 40:60.

5. A mixture according to Claim 1, which comprises the compounds of formulae I and II in a 1:1 molar ratio range.

6. A mixture according to any one of the preceding claims, wherein the R1,s are Rr's, where each RI, independently, is hydrogen or methyl,

7. A mixture according to any one of the preceding claims, wherein the R2,s are R2's, where each R2, independently, is hydrogen, cyano, chlorine, methyl, methoxy or ethoxy.

8. A mixture according to any one of the preceding claims, wherein the R3'S are Fl3'S, where each Fl3,, independently, is hydrogen, chlorine, methyl, methoxy or ethoxy.

9. A mixture according to any one of the preceding claims, wherein, in the compound of formulae I and II, the R 's are Rr's, as defined in Claim 6, the Fl2,s are P2"S, as defined in Claim 7, and the Fl3,s are R"s, as defined in Claim 8.

1 0. A mixture according to any one of Claims 1 to 8, wherein R2,s are R2"s, where each R2', independently, is hydrogen, chlorine, methyl or methoxy.

11. A mixture according to any one of Claims 1 to 8 or 10, wherein the Fl3,s are R3"s, where each R3', independently, has one of the significances of R2', as defined in Claim 10.

12. A mixture according to any one of the preceding claims, wherein the X's are both OH or are both NH2.

13. A mixture according to Claim 12, wherein the X's are OH.

14. A mixture according to any one of the preceding claims, wherein, in the compound of formula II, the carboxylic acid group is in the 2-position.

1 5. A mixture according to any one of the preceding claims, wherein the Fl2,s are P2,,,s and the R3,s are hydrogen.

1 6. A mixture according to any one of the preceding claims, wherein the R,'s are hydrogen.

1 7. A mixture according to any one of the preceding claims, wherein the fl2,s and R3's are indentical.

1 8. A mixture according to Claim 1, of symmetrical and asymmetrical 1:2 cobalt complexes of compounds of the formulae

which complexes are present in a 1:1 molar ratio.

1 9. A mixture according to any one of the preceding claims, wherein the complexes are in the sodium salt form with respect to the complex anion-neutralizing cation of each 1:2 cobalt complex and to the carboxylic acid group in a compound of formula II.

20. A complex mixture according to any one of Examples 2 to 30.

21. A process for the production of a mixture of symmetrical and asymmetrical 1:2 cobalt complexes of the compounds of formulae I and II, as defined in Claim 1, comprising reacting a mixture of the compounds of formulae I and II with a cobalt donating compound.

22. A process for the production of a mixture of symmetrical and asymmetrical 1:2 cobalt complexes of the compounds of formulae I and II, substantially as hereinbefore described with reference to any one of Examples 1. to 30.

23. A mixture whenever obtained by a process according to Claim 21 or Claim 22.

24. A process for dyeing or printing substrates dyeable with anionic dyes comprising employing a mixture according to any one of Claims 1 to 20 or 23 as dyeing or printing agent.

25. A process according to Claim 24, in which the substrate consists of or comprises natural or synthetic polyamides, polyurethanes, basic modified polyolefins, leather and anodically oxidized aluminum.

26. A process for dyeing or printing substantially as hereinbefore described with reference to any one of Application Examples A or B.

27. Dyed or printed substrates whenever obtained by a process according to any one of Claims 24 to 26.