GB1578733A

GB1578733A - Halogen- and cyano-containing mono-azo dyestuff compositions

Info

Publication number: GB1578733A
Application number: GB2228476A
Authority: GB
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Imperial Chemical Industries Ltd
Priority date: 1977-05-23
Filing date: 1977-05-23
Publication date: 1980-11-05

Description

(54) HALOGEN- AND CYANO-CONTAINING MONO-AZO DYESTUFF COMPOSITIONS (71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Chemical House, Millbank, London, SWIP 3JF, a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to dyestuff compositions, to their method of manufacture and to their use for colouring textile fibres, in particular, synthetic fibres and especially polyester fibres.

According to the present invention we provide a dyestuff composition which comprises a stable mixture of a dyestuff of the formula: X-A-N=N-B wherein X is iodine, bromine or chlorine; A is an optionally substituted aromatic or heteroaromatic radical; and B is an N-substituted p-aminophenyl radical which may be further substituted in the nucleus and of an identical dyestuff except that X is cyano, each dyestuff comprising at least 20 /" of the total weight of the composition.

Preferably X is in an ortho position to the azo group. Of particular interest are compositions of azo dyes devoid of water solubilising groups, particularly those wherein A is a substituted phenyl radical, an optionally substituted thiophene radical attached at the 2-position to the azo group, or a benzoisothiazolyl-l,2 or -2,1 radical.

The constituent dyestuffs preferably have one of the following general formulae:

wherein X has the meaning hereinbefore defined, T is hydrogen, cyano, halogen, nitro or a radical of the formula:

Y is hydrogen, lower alkyl, lower alkoxy, or halogen; Z is hydrogen, lower alkyl, lower alkoxy, halogen, or acylamino, particularly acetylamino, propionylamino or A-chloropropionylamino; R1 is lower alkyl or substituted lower alkyl, for example, hydroxylower alkyl, cyano lower alkyl, phenyl lower alkyl, lower alkoxycarbonyl lower alkyl and acyl amino lower alkyl, R2 is hydrogen, lower alkyl or substituted lower alkyl, for example, hydroxylower alkyl and lower alkoxycarbonyl lower alkyl; and, in particular, either or both R, and R2 are

wherein R8 and R9 are independently methyl or hydrogen and R10 is lower alkyl or (CH2)nCOOR,1 wherein n is 2 to 4 and R1, is lower alkyl, provided that if two substituents R8 are present in the same molecule at least one of them is hydrogen; R3 is hydrogen, lower alkyl, phenyl, lower alkylphenyl, halophenyl, lower alkoxyphenyl or dihalophenyl; and either R4 is lower alkyl; and R5 is lower alkoxycarbonyl; or R4 and R5 together with the carbon atoms to which they are attached form a benzene ring which may bear lower alkyl or lower alkoxy substituents;

wherein X, Y, Z, R, and R2 have the meanings hereinbefore defined; R6 is hydrogen, aryl, nitro, lower alkyl, optionally substituted aryl, or optionally substituted carbo lower alkoxy, and R7 is hydrogen, lower alkyl, optionally substituted aryl, nitro, cyano, chlorine, bromine, optionally substituted carbo lower alkoxy, optionally substituted aryloxycarbonyl or carbonamido, provided that R6 and R7 are not both hydrogen or

wherein Y, Z, R, and R2 have the meanings hereinbefore defined.

By the terms "lower alkyl" and "lower alkoxy" we mean alkyl and alkoxy radicals respectively containing from 1 to 4 carbon atoms.

Of particular interest are compositions of the dyestuffs of formula (a) wherein T is cyano, halogen, or nitro; Y is hydrogen; Z is acetylamino and R, and R2 are lower alkyl.

The compositions of the invention, in which each of the constituent dyestuffs comprises at least 20% of the total weight of the composition, generally exhibit better all-round dyeing properties than the individual constituent dyestuffs. In particular the depth of shade obtained when these compositions are used to dye polyester fibre is greater than that obtained from an equivalent weight of either of the individual dyestuffs.

Specifically we would mention the compositions which comprise (i) the dyestuffs

in the approximate proportion of 20 to 80 parts by weight; (ii) the dyestuffs I and 11 in the approximate proportion of 40 to 60 parts by weight; (iii) the dyestuffs

and II in the approximate proportion of 65 to 35 parts by weight and (iv) the dyestuffs Ill and II in the approximate proportion of 50 to 50 parts by weight.

The compositions of the invention may be obtained simply by mixing the constituent dyestuffs. They are, however conveniently prepared by a process in which the halogen-containing dyestuff is partially converted to the equivalent cyano-containing dyestuff.

Thus according to a further embodiment of our invention we provide a process for the manufacture of a dyestuff composition which comprises reacting a desired proportion of a first dyestuff of the formula X-A-N=N-B wherein X is iodine, bromine or chlorine, and A and B have the meanings hereinbefore defined, with cuprous cyanide, a cyano-cuprate complex or another metal cyanide in the presence of a copper compound to form in admixture with the unreacted proportion of the dyestuff a second dyestuff of the same formula except that X is cyano, the reaction being monitored continuously or at intervals and terminated when the desired proportion of the first dyestuff has reacted.

The reaction may be carried out in an organic solvent or in aqueous medium using any of the known processes, for instance those described in UK Patent Specifications Nos. 1,125,683, 1,184,825, 1,387,728, 1,412,922, 1,438,374 and 1,444,524. Preferably, the reaction is carried out in the presence of a phase transfer catalyst as described in our copending British Application No. 22283/76 (Serial No.

1,578,732) or, when the reaction is carried out in aqueous medium, in the presence of water immiscible organic solvent optionally together with a phase transfer catalyst as described in our co-pending British Application No. 22285/76 (Serial No. 1,578,731). The presence of these materials tends to increase the reaction rate or enables the reaction to be carried out at lower temperatures.

Thus, conveniently, the halogen-containing dye which is to be converted to the cyano derivative and cuprous cyanide, or other metal cyanide, particularly an alkali metal cyanide, and a copper compound, preferably a copper (I) compound, are stirred either in an organic solvent together with a phase transfer catalyst or in aqueous suspension/solution together with a phase transfer catalyst and/or a water immiscible solvent at a temperature of from 15"C to 1000C. If desired higher temperatures of up to 2000C may be used to increase further the reaction rate. The progress of the reaction is monitored by, for example, withdrawing samples of the reaction mixture at intervals and determining the relative proportion of constituent dyestuffs by a chromatographic technique, such as thin layer chromatography.

When the reaction has proceeded to the desired extent, the reaction is terminated by isolating the mixtures of dyes by filtration and washing to remove copper salts with, for example, aqueous ammonia or potassium cyanide solution. Where a solvent is used in the process this is conveniently removed by steam distillation before the reaction mixture is filtered. The reaction takes between 0.25 and 20 hours, usually between 1 to 5 hours, depending on the reaction temperature and the structure of the particular dyestuffs involved.When the reaction is carried out in aqueous suspension in the presence of a phase transfer catalyst agitation is preferably vigorous, and since the rate of reaction will depend inter alia on the particle size of the reactants it is sometimes advantageous to subject the reactants to mild grinding during reaction for instance by agitating the reaction mixture in the presence of glass beads. A water immiscible solvent may be used in addition to or instead of the grinding process.

Thus cuprous cyanide itself need not directly be added to the reaction mixture.

It is sufficient to add substances which form cuprous cyanide under the conditions of the reaction. Normally the about of cuprous cyanide used will not be less than the equivalent of the halogen to be replaced. Further, as has been said, it is also possible to use and it is preferred to use copper compounds, including cuprous cyanide itself, in catalytic amount, that is in amount less than the stoichiometric equivalent to the halogen to be replaced (from 0.005 moles/mole replaceable halogen upwards), the cyanide being supplied by an alkali metal cyanide. A further refinement is to add the metal cyanide, preferably in aqueous solution, gradually as the reaction progresses. This minimises any degradation of the azo dyestuff by high concentrations of the metal cyanide.

If a phase transfer catalyst is used in the process this will usually be present in the quantity of from 0.1 to 25 /" of the weight of the halogen-containing dye, preferably from 1 to 12%. If a water immiscible solvent is used in the process the amount present is usually such that the solvent to water weight ratio is between 5 and 1 and 1 to 1000 and the total quantity of water and solvent used is chosen to give a readily stirrable mixture with the dyestuff at the reaction temperature. It is not necessary that the amount of organic solvent used should completely dissolve the dyestuff. Useful results are obtained by using an organic solvent to dyestuff weight ratio of between 1 to 1 and 1 to 100 and preferably between 1 to 1 and 1 to 10.

The dyestuff compositions of the invention can be applied to the textile materials by any conventional method. Particularly useful for dyeing synthetic textile materials, especially aromatic polyester textile materials, are those compositions in which the constituent dyestuffs are disperse dyestuffs devoid of water solubilising groups. These disperse dyestuff compositions in the form of aqueous dispersions can be applied by dyeing, padding or printing processes using the conditions and other additives which are conventionally used, and optionally in combination with other dyestuffs. Alternatively the dyestuff compositions can be applied by solvent methods, for example by applying to the material a solution or dispersion of the composition in a suitable solvent optionally containing a minor amount of water at elevated temperature.

The invention is illustrated but not limited by the following examples in which parts and percentages are by weight.

Example 1 4.79 Parts of the violet dyestuff of formula I (see below), 1.18 parts of cuprous cyanide 0.5 parts of octyl tributyl ammonium bromide, and 178 parts of water are stirred and heated at 1000C. It is shown by thin layer chromatography that conversion to the greenish blue dye of formula II (see below) reaches about 65 /" in 40 minutes and 80% after 3 hours. At this stage the dye which is a mixture of I and II in the approximate proportion of 20:80 is collected by filtration, and is washed with aqueous ammonia or potassium cyanide solution to remove copper salts.It dyes polyester in greenish blue shades from an aqueous dispersion.

Example 2 A mixture comprising 4.79 parts of the dyestuff of Example 1, 30 parts of water, 0.5 parts of octyl tributyl ammonium bromide, 2.4 parts of nitrobenzene and 0.2 parts of cuprous chloride is stirred and heated under reflux. A total of 0.4 parts of sodium cyanide is added during I hour after which time conversion of the bromo dyestuff I to the the cyano dyestuff II reaches 60%. The nitrobenzene is removed by steam distillation and the dye is collected by filtration, stirred for 4 hours with 100 parts of 20% aqueous ammonia solution,-recollected, washed with water and dried.

The dyestuff thus obtained, which is a mixture of the dyestuffs I and Il in the approximate proportion of 40:60, dyes polyester textile materials in blue shades, building up to strong navy shades.

Example 3 A mixture comprising 4.35 parts of the violet dye of formula Ill (see below), 1.47 parts of cuprous cyanide, 0.5 parts of octyl tributyl ammonium bromide and 150 parts of water is stirred under reflux. Conversion to the cyano dye of formula 11 reaches 35 in 20 hours. The dyestuff obtained by filtration of the reaction suspension dyes polyester textile materials in blue shades which build up to strong reddish navy shades.

Example 4 A mixture comprising 4.35 parts of the violet dyestuff II of Example 3, 1.18 parts of cuprous cyanide, 32 parts of water, 0.07 parts of a commerical non-ionic surfactant which is a condensation product of a mixture of cetyl and stearyl alcohols with 17 moles of ethylene oxide, 4.62 parts of pyridine and 0.5 parts of nitrobenzene is stirred and heated under reflux. After 3 hours, conversion to the greenish blue dyestuff of formula II reaches 50%. Both pyridine and nitrobenzene are recovered by steam distillation, and the dyestuff composition which is a mixture of III and II in the approximate proportion of 50:50 is isolated as in Example 2.

WHAT WE CLAIM IS: 1. A dyestuff composition which comprises a stable mixture of a dyestuff of the formula: X-A-N=N-B wherein X is iodine, bromine or chlorine; A is an optionally substituted aromatic or heteroaromatic radical; and B is an N-substituted p-aminophenyl radical which may be further substituted in the nucleus; and of an identical dyestuff except that X is cyano, each dyestuff comprising at least 20% of the total weight of the composition.

2. A composition as claimed in claim 1 in which X is ortho to the azo group.

3. A composition as claimed in claims 1 or 2 in which the dyestuffs are devoid of water solubilising groups.

4. A composition as claimed in any one of the preceding claims in which A is a substituted phenyl radical, an optionally substituted thiophene radical attached at the 2-position to the azo group, or a benzoisothiazolyl-1,2 or -2,1 radical.

5. A composition as claimed in any one of claims 1 to 3 in which the dyestuffs have the formula:

wherein T is hydrogen, cyano, halogen, nitro or a radical of the formula

Y is hydrogen, lower alkyl, lower alkoxy, or halogen; Z is hydrogen, lower alkyl, lower alkoxy, halogen, or acylamino; R, is lower alkyl or substituted lower alkyl; R2 is hydrogen, lower alkyl or substituted lower alkyl; R3 is hydrogen, lower alkyl, phenyl, lower alkylphenyl, halophenyl, lower alkoxyphenyl or dihalophenyl; and either R4 is lower alkyl; and R5 is lower alkoxycarbonyl; or R4 and R5 together with the carbon atom to which they are attached form a benzene ring which may bear lower alkyl or lower alkoxy substituents.

6. A composition as claimed in claim 5 in which either or both R1 and R2 are

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. Example 4 A mixture comprising 4.35 parts of the violet dyestuff II of Example 3, 1.18 parts of cuprous cyanide, 32 parts of water, 0.07 parts of a commerical non-ionic surfactant which is a condensation product of a mixture of cetyl and stearyl alcohols with 17 moles of ethylene oxide, 4.62 parts of pyridine and 0.5 parts of nitrobenzene is stirred and heated under reflux. After 3 hours, conversion to the greenish blue dyestuff of formula II reaches 50%. Both pyridine and nitrobenzene are recovered by steam distillation, and the dyestuff composition which is a mixture of III and II in the approximate proportion of 50:50 is isolated as in Example 2. WHAT WE CLAIM IS:

1. A dyestuff composition which comprises a stable mixture of a dyestuff of the formula: X-A-N=N-B wherein X is iodine, bromine or chlorine; A is an optionally substituted aromatic or heteroaromatic radical; and B is an N-substituted p-aminophenyl radical which may be further substituted in the nucleus; and of an identical dyestuff except that X is cyano, each dyestuff comprising at least 20% of the total weight of the composition.

2. A composition as claimed in claim 1 in which X is ortho to the azo group.

wherein T is hydrogen, cyano, halogen, nitro or a radical of the formula

6. A composition as claimed in claim 5 in which either or both R1 and R2 are

wherein R8 and R9 are independently methyl or hydrogen and R10 is lower alkyl or (CH2)nCOOR,1 wherein n is 2 to 4 and R is lower alkyl, provided that if two substituents Ra are present in the same molecule at least one of them is hydrogen.

7. A composition as claimed in any one of claims I to 3 in which the dyestuffs have the formula

wherein Y, Z, R, and R2 have the meanings defined in claim 5; R6 is hydrogen, aryl, nitro, lower alkyl, optionally substituted aryl, or optionally substituted carbo lower alkoxy; and R7 is hydrogen, lower alkyl, optionally substituted aryl, nitro, cyano, chlorine, bromine, optionally substituted carbo lower alkoxy, optionally substituted aryloxycarbonyl or carbonamido, provided than R6 and R7 are not both hydrogen.

8. A composition as claimed in any one of claims I to 3 in which the dyestuffs have the formula:

wherein Y, Z, R, and R2 have the meanings defined in claim 5.

9. A composition as claimed in claim 5 in which T is cyano, halogen or nitro; Y is hydrogen; Z is acetylamino and R, and R2 are lower alkyl.

10. A dyestuff composition comprising a first dyestuff of the formula:

wherein X is bromine or chlorine, and a second dyestuff of the same formula except that X is cyano, the first and second dyestuffs being present in the proportion of 20 to 80 parts by weight or 40 to 60 parts by weight when X in the first dyestuff is bromine, or of 50 to 50 parts by weight or 65 to 35 parts by weight when X in the first dyestuff is chlorine.

11. A dyestuff composition substantially as herein described with reference to any one of Examples I to 4.

12. A process for the manufacture of a dyestuff composition which comprises reacting a desired proportion of a first dyestuff of the formula X-A-N=N-B wherein X is iodine, bromine or chlorine; A is an optionally substituted aromatic or heteroaromatic radical; and B is an N-substituted p-aminophenyl radical which may be further substituted in the nucleus; with cuprous cyanide, a cyano-cuprate complex or another metal cyanide in the presence of a copper compound, to form in admixture with the unreacted proportion of the dyestuff a second dyestuff of the same formula except that X is cyano, the reaction being monitored continuously or at intervals and terminated when the desired proportion of the first dyestuff has reacted.

13. A process as claimed in claim 12 in which the reaction is carried out in the presence of a phase transfer catalyst or, when the reaction is carried out in aqueous medium, in the presence of a water immiscible organic solvent optionally together with a phase transfer catalyst.

14. A process as claimed in claim 13 in which the phase transfer catalyst is present in the quantity of from 0.1 to 25% of the weight of the halogen containing dye.

15. A process as claimed in claim 14 in which the phase transfer catalyst is present in the quantity of from 1 to 12% of the weight of the dyestuff.

16. A process as claimed in claim 13 in which the water immiscible solvent and dyestuff are present in the ratio of between 1 to 1 and 1 to 100, respectively.

17. A process as claimed in claim 13 in which the water immiscible solvent and dyestuff are present in the ratio of between 1 to 1 and 1 to 10, respectively.

18. A process as claimed in any one of claims 1 to 17 in which the reaction is monitored by withdrawing samples of the reaction mixture at intervals and determining the relative proportion of constituent dyestuffs by a chromatographic technique.

19. A process as claimed in any one of claims 12 to 18 in which the reaction is terminated by filtering and washing the mixture of dyes.

20. A process as claimed in any one of claims 12 to 19 in which the other metal cyanide is an alkali metal cyanide.

21. A process as claimed in any one of claims 12 to 20 in which the copper compound is a copper (I) compound.

22. A process as claimed in any one of claims 12 to 21 in which the copper compound is used in catalytic amount.

23. A process as claimed in any one of claims 12 to 22 in which the other metal cyanide is added gradually as the reaction progresses.

24. A process as claimed in claim 23 in which the metal cyanide is added as an aqueous solution.

25. A process as claimed in claim 12 substantially as herein described with reference to any one of the Examples.

26. Dyestuff compositions whenever produced by a process as claimed in any one of claims 12 to 25.

27. A process for dyeing textile materials which comprises applying a dyestuff composition as claimed in any one of claims 1 to 10 and 26 to a textile material by any conventional dyeing method.

28. A process as claimed in claim 27 in which the textile material is synthetic and the dyestuff composition is devoid of water solubilising groups.

29. A process as claimed in claim 28 in which the synthetic material is an aromatic polyester material.

30. Textile materials whenever dyed by a process as claimed in any one of claims 27 to 29.