EP1966327A2

EP1966327A2 - Reactive azo compounds

Info

Publication number: EP1966327A2
Application number: EP06779157A
Authority: EP
Inventors: Hunter Renfrew
Original assignee: ATUL Ltd
Current assignee: ATUL Ltd
Priority date: 2005-08-31
Filing date: 2006-08-18
Publication date: 2008-09-10
Also published as: WO2007026116A2; WO2007026116A3; GB0616173D0

Abstract

A compound having the formula as shown in Formula (1), where each of R1, R2, R3 is H or an alkyl group; X is nitrogen or C-B where B is H, Cl or a methyl group; D and D1 are organic residues, which may be the same or different; and E is an organic residue or a group of the Formula (2), where R4, R5 are each hydrogen, methyl, methoxyl or SO3H, is useful in colouring cellulosic fabrics, and may be used to colour blends of cellulosic fibres with fibres such as polyester which are dyed using disperse dyes in a single-bath, single-stage operation.

Description

Compound

This invention relates to compounds, more particularly to compounds useful in treating, especially colouring fabrics as by dyeing or printing.

Problems arise in colouring certain fibres, such as natural or regenerated cellulosic fibres, particularly when in combination with synthetic fibres such as polyester fibres. The conditions under which the polyester fibres are coloured using disperse dyes are usually different from the conditions required for the colouring of cellulosic fibres using conventional reactive dyes, which require highly alkaline conditions unsuitable for disperse dyes.

US4686286 discloses disazo reactive dyestuffs for cellulose fibres which can be used in a single-bath, single-stage dyeing operation on cellulose/polyester blends at lower pH levels.

The present invention provides compounds useful inter alia in colouring cellulosic fibres in blends with synthetic fibres dyed with disperse dyes, which are capable of a wider and deeper colour range than the disazo dyestuffs of US4686286.

The invention comprises a compound having the formula:

(Formula 1) where: each of R-i, R₂, R₃ is H or an alky! group; X is nitrogen or C-B where B is H, Cl or a methyl group; D and D1 are organic residues, which may be the same or different; and E is an organic residue or a group of the formula:

(Formula 2) where R₄, R₅ are each hydrogen, methyl, methoxyl or SO₃H.

The organic residues D, D1 and E may be the same or different, and may be residues of monoazo, disazo, anthraquinone, triphendioxazine, formazan or metal phthalocyanine dyes.

'B' may be H, Cl, methyl and substituted.

Any two or all three of R-i, R₂, R₃ may be similar.

Ε¹ may be the residue of a monoazo or disazo dye and at least one of D, D1 and E may contain a fibre reactive group Z. Where 'E' is the residue of a monoazo or disazo dye, at least one of D, D1 and E may contain a fibre reactive group Z.

'Z' may be -SO₂-Y or -NHCO(CH₂)_a- SO₂-Y, -CONH(CH₂)_b-SO₂-Y, -CONHCH₂CH₂OCH₂CH₂ -SO₂-Y, -NHCOCH(hal)CH₂hal, or -NHCOC(hal)=CH₂.

'hal' may be selected from Cl and Br. 'a' may be 2, 3 or 4. 'b' may be 2, 3 or 4.

¹Y' may be vinyl. ¹Y' may be a radical - CH₂CH₂-U, where U is a group removable under alkaline conditions.

¹E' may be a group of formula 2 and at least one of D and D1 may contain a fibre reactive group Z. T may be -SO₂-Y or NHCO(CH₂)_a-SO₂-Y.

R4 and R5 may be selected from the group hydrogen, methyl, methoxyl and SO₃H.

The compounds may be used for colouring materials, especially fibre materials and more especially amide group-containing materials and particularly for colouring natural or regenerated fibre materials, as by dyeing or printing, and the invention comprises the compounds when so used.

The invention also comprises a method for colouring a material, comprising applying to the material a compound as above set forth under neutral conditions.

The invention comprises also a method for colouring both cellulosic and polyester fibres simultaneously, comprising using a reactive dye comprising a compound as above set forth together with a disperse dye.

The invention also comprises a method for making a compound as set forth above comprising the steps of: reacting 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid twice with cyanuric chloride to make a first reaction product (the first reaction); reacting the first reaction product with 2,4-diaminobenzenesulphonic acid to make a second reaction product (the second reaction) adding a diazonium salt to the second reaction product.

The first reaction may be carried out in aqueous medium under acidic conditions. The acidic conditions may be adjusted to pH 3.0 as by the addition of sodium carbonate, and the reaction may be carried out at 3O⁰C. The second reaction may be carried out at 7O⁰C.

The compounds are useful, when the functional groups include monoazo, disazo anthraquinone, triphendioxazine, formazan or metal phthalocyanine dye residues, for colouring cellulosic textiles, especially in blends with polyester, as they will dye under like conditions to disperse dye conditions for polyester, namely under neutral pH

Example 1

To a solution of 63.8 parts 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid in 200 parts water at O⁰C and pH 7.0 was added a slurry of 18.5 parts cyanuric chloride in 100 parts water at O⁰C in the course of 60 minutes. The mixture was stirred at 3⁰C for 3 hours and a solution of 2N-sodium carbonate was added to adjust the pH to 3.0. The reaction mixture was heated to 3O⁰C and the resultant suspension stirred for four hours whilst maintaining the pH at 3.0. A solution of 18.0 parts 2,4-diaminobenzenesulphonic acid in 150 parts water, at pH 5.0 was added, the reaction mixture being stirred for one hour and then heated at 7O⁰C for 10 hours. To this solution was added a diazonium salt solution prepared as follows:

4-β-sulphatoethylsulphonylaniline (82.9 parts), hydrochloric acid (30% strength, 38.4 parts, ice water (900 parts) and 4N-sodium nitrite (74.6 parts) at 0-5⁰C were mixed together. The mixture was stirred for 45 minutes at 0-5⁰C before destroying excess nitrous acid by addition of sulphamic acid. The coupling reaction mixture was stirred for two hours maintaining pH 5.0 with 2N-sodium carbonate solution and further stirred for two hours.

The dye thus obtained has a formula:

Application of the dye to cellulose by an exhaust dyeing procedure, at 8O⁰C, in the presence of salt and alkali, gave deep red shades with good all round fastness.

Using the basic formula, the chromophoric load can be maximised - the molecule can have three chromophoric components, as compared to two in the dyestuff of US 4868268, and the components can be the same or mixed to give different shades and depths of shade. A range of colours including yellow, orange, red, blue and navy can be produced.

Example 2

To 8-amino-2(o-sulphonaphth-2'-yl)-hydrazino-1 -oxo-1 ,2-dihydronaphthalene- 3,6-disulphonic acid (31 g) in water (60OmIs), at 0-5⁰C, was added cyanuric chloride (4.7g) and the reaction mixture stirred for 2hrs. Sodium hydroxide was added to give a pH of 3.5, the temperature raised to 35⁰C, and stirring continued for a further 10hrs. 2,4-Diaminobenzenesulphonic acid (4.7g) was then added, the pH adjusted to 6.0, the temperature raised to 7O⁰C and the reaction continued for a further 15hrs. On cooling to 0-5⁰C, a suspension of the diazonium salt of p-aminophenyl-β-sulphatoethylsulphone (7g), prepared in the usual way, was added and stirring continued until the coupling reaction was complete. The addition of sodium chloride (20% w/v) gave the desired product (56g) as a red solid of structure:

Application to cotton by a cold-pad-batch procedure gave deep red shades with good all-round fastness properties. The dye also showed good build-up when applied to cellulosic fibres, at 13O⁰C, under neutral fixation conditions, giving red shades with good wet fastness properties.

The following red dyes of general formula (3) were made in a similar manner, and the intermediates A, B, D, and E used are shown in Table 1.

(3)

Table 1: Examples 1-10

Example 11

To 8-amino-2(o-sulphonaphth-2'-yl)-hydrazino-1 -oxo-1 ,2-dihydronaphthalene- 3,6-disulphonic acid (15.5g) in water (80OmIs), at 0-5⁰C, was added cyanuric chloride (4.7g) and the reaction mixture stirred for 2hrs. 6-Methylamino-2(1',5'~ disulphonaphth-2'-yl)-hydrazino-1 -oxo-1 ,2-dihydronaphthalene-3-sulphonic acid (15.6g) was added, the pH adjusted to 6.5, the temperature increased to 35⁰C, and stirring continued for a further 10hrs. 2,4-Diaminobenzenesulphonic acid (4.7g) was then added, the pH adjusted to 6.0, the temperature raised to 7O⁰C and the reaction continued for a further 15hrs. On cooling to 0-5⁰C, a suspension of the diazonium salt of p-aminophenyl-β-sulphatoethylsulphone (7g), prepared in the usual way, was added and stirring continued until the coupling reaction was complete. The addition of sodium chloride (20% w/v) gave the desired product (36g) as a red solid of structure:

The dye gave yellowish-red shades on cotton with good all-round fastness properties.

The following dyes of general formula (4) were made in a similar manner, and the intermediates A, B, D, and E used are shown in Table 2.

(4)

Table 2: Examples 12-17

O₂CH₂CH₂OSO₃H

Example 18

To 2-β-carboxyethylamino-4-aminobenzenesulphonic acid (13.5g) in water (50OmIs), at 0-5⁰C, was added with stirring, cyanuric chloride (3.1g), the pH adjusted to 4.0 and the reaction mixture stirred for 2hrs while maintaining the pH at 4-5. The temperature was raised to 35⁰C, the reaction continued for a further 6hrs and finally the temperature was increased to 70 ⁰C and maintained till a negative Ehrlich's test was given. The solution was cooled to 0-5 ⁰C and a suspension of the diazonium salt of p-aminophenyl-β-sulphatoethylsulphone (14.2g), prepared in the usual way, was added and stirring continued until the coupling reaction was complete. The addition of sodium chloride (20% w/v) gave the desired product (36g) as an orange solid of structure:

Application to cotton by an exhaustion process gave strong yellow shades with good all-round fastness properties. The dye also showed good build-up when applied to cellulosic fibres, at 13O⁰C, under neutral fixation conditions, giving yellow shades with good wet fastness properties.

The following yellow dyes of general formula (5) were made in a similar manner, and the intermediates A₁ B, D, and E used are shown in Table 3. (5)

Table 3: Examples 19-24

Example 25

To 6-methylamino-2(1 ',5'-disulphonaphth-2'-yl)-hydrazino-1 -oxo-1 ,2- dihydronaphthalene-3-sulphonic acid (31.2g) in water (1 litre), at 0-5⁰C, was added cyanuric chloride (4.7g), and the reaction mixture stirred for 2hrs at pH 6- 6.5. The temperature was raised to 35 ⁰C and stirring continued for a further 10hrs. 2,4-Diaminobenzenesulphonic acid (4.7g) was then added, the temperature raised to 7O⁰C and the reaction continued for a further 15hrs. On cooling to 0-5⁰C, a suspension of the diazonium salt of p-aminophenyl-β- sulphatoethylsulphone (7g), prepared in the usual way, was added and stirring continued until the coupling reaction was complete. The addition of sodium chloride (20% w/v) gave the desired product (36g) as an orange solid of structure:

The dye gave orange shades on cotton, viscose and lyocell with good all-round fastness properties.

The following dyes of general formula (6), were made in a similar manner, and the intermediates A, B, and D used are shown in Table 4.

(6) Table 4

Example No. A B Ri R₂

26 2-naphthyl- 2-naphthyl- aniline-4-β- Me Me carboxyethyl amiπe-1 ,5-di- amine-1,5-di- sulphatoethyl- disulphonic acid disulphonic acid sulphone

27 2-naphthyl- 2-naphthyl- aniline-3-β- H H H amine-1 ,5-di- amine-1 ,5-di- sulphatoethyl- disulphonic acid disulphonic acid sulphone

28 2-naphthyl- 2-naphthyi- 3-(2'-vinyl- Me Me H amine-1 ,5-di- amine-1 ,5-di- sulphonyl)-N- disulphonic acid disulphonic acid θthylamidoaniline

29 2-naphthyl- 2-naphthyl- 3-(2'- β-vinyl- Me Me H amine-1,5-di- amine-1 ,5-di- sulphonyl)prop- disulphonic acid disulphonic acid ionamido- 6-sulphoaniline

30 2-naphthyl- 2-naphthyl- p-aminophenyl- Me Me H amine-1 ,5-di- amine-1, 5-di- vinylsuiphone disulphonic acid disulphonic acid

31 2-naphthyl- 2-naphthyl- 3-acrylamido- Me Me H amine-1 ,5-di- amine-1 ,5-di- 6-sulpho- disulphonic acid disulphonic acid aniline

32 2-methoxy-5- 2-methoxy-5- 2-methoxy-5- H H H β-sulphatoethyl- β-sulphatoethyl- β-sulphatoethyl- sulphonyl- sulphonyl- sulphonyl- aniline aniline aniline

33 aniline-2,5- aniline-2,5- aniline-4-β- Me Me H disulphonic disulphonic sulphatoethyl- acid acid sulphone

34 2,5-disulpho- 2,5-disulpho- aniline-4-β- Me Me H

4-methyl- 4-methyl- sulphatoethyl- aniline aniiine sulphone

Example 35

To 7-amino-2-(2',5'-disulphophen-1 '-yl)hydrazino-1 -oxo-1 ,2-dihydronaphthalene- 3-sulphonic acid (28.5g) in water (800 mis), at 0-5⁰C, was added cyanuric chloride (4.7g), and the reaction mixture stirred for 2hrs at pH 3. The temperature was raised to 35 ⁰C and stirring continued for a further 10hrs. 2,4-Diamino- benzenesulphonic acid (4.7g) was then added, the temperature raised to 7O⁰C and the reaction continued for a further 15hrs. On cooling to 0-5⁰C, a suspension of the diazonium salt of p-aminophenyl-β-sulphatoethylsulphone (7g), prepared in the usual way, was added and stirring continued until the coupling reaction was complete. The addition of sodium chloride (20% w/v) gave the desired product (31 g) as an orange solid of structure:

Example 36

To 1-amino-2-sulpho-4-(3'-amino-4'-sulpho)anilino-anthraquinone (26.2g) in water (1 litre), at 0-5⁰C₁ was added cyanuric chloride (4.7g), and the reaction mixture stirred for 2hrs at pH 5. The temperature was raised to 35⁰C and stirring continued for a further 12 hrs. 2,4-Diaminobenzenesulphonic acid (4.7g) was then added, the temperature raised to 7O⁰C and the reaction continued for a further 15hrs. On cooling to 0-5⁰C, a suspension of the diazonium salt of p- aminophenyl-β-sulphatoethylsulphone (7g), prepared in the usual way, was added and stirring continued until the coupling reaction was complete. The addition of sodium chloride (15% w/v) gave the desired product (27g) as a dark solid of structure:

The dye gave green shades on cotton, viscose and lyocell with good all-round fastness properties.

Example 37

To 3-ureido-4-(3'6'8'-trisulphonaphth-2'-yl)azoaniIine (15.3g) in water (1 litre), at 0-5⁰C, was added cyanuric chloride (1.6g), and the reaction mixture stirred for 2hrs at pH 5. 2,4-Diaminobenzenesulphonic acid (9.4g) was added, the pH adjusted to 6 and the temperature raised to 35⁰C for 4 hrs. The temperature was finally raised to 7O⁰C and the reaction continued for a further 15hrs to give the desired coupling component. On cooling to 0-5⁰C, a suspension of the diazonium salt of p-aminophenyl-β-sulphatoethylsulphone (14.4g), prepared in the usual way, was added and stirring continued until the coupling reaction was complete. The addition of sodium chloride (15% w/v) gave the desired product (22g) as an orange solid of structure:

The dye gave yellow shades on cotton with good all-round fastness properties.

The following dyes of general formula (7), were made in a similar manner, and the intermediates A, B, D, E, F, and G used are shown in Table 5.

(7)

Table 5

Example No. A B D E F G

38 CONH₂ carboxyethyl SO₃H aniline-4-β-sulphatoethyl- carboxyethyl SO₃H sulphone

39 ditto hydroxyethyl ditto ditto hydroxyethyl ditto

40 ditto carboxymethyl ditto aniline-3-β-sulphatoethyl- carboxymethyl ditto sulphone

41 ditto carboxyethyl H ditto carboxyethyl H

42 COCH₃ H SO₃H ditto H SO₃H

43 ditto carboxyethyl ditto aniline-4-β-sulphatoethyl- carboxyethyl ditto sulphone

44 ditto ditto ditto ditto . H ditto

Example 45

To 4-(2'-sulphatoethylsulphonyl)aniline (53.5g), 30% hydrochloric acid (921 mis) and ice water (600 mis)] at 0-5⁰C was added 4N-sodium nitrite (48.6 g). The mixture was stirred for 45 mins and sulphamic acid solution (10%) was added to remove excess nitrous acid. A solution of 1-amino-8-hydroxy-naphthalene-3,6- disulphonic acid (60.5g), at 0-5⁰C, was added to the above suspension of diazonium salt in the course of 60 minutes and stirred for a further 2 hours at 0- 5⁰C.

A solution of 2,4-diaminobenzenesulphonic acid (18.8g) at 18-20⁰C was added to a slurry of cyanuric chloride (18.5g) and ice water (90 mis) in the course of 60 mins. The mixture was stirred for 1 hour at 2-4°C. An additional solution of 2,4- diaminobenzenesulphonic acid (18.8g) at 18-2O⁰C was added over 30 minutes, the pH adjusted to 3.5, the temperature to 25°C and the reaction mixture stirred for 4 hours while maintaining the pH 3.5-3.8. 4-(2'-Sulphatoethylsulphonyl)aniline (26.7 g) was added, the temperature was raised to 7O⁰C, while maintaining pH 2.8-3.2 and stirring continued for 6 hours to give the tricondensed product. The resultant solution was cooled to 0⁰C, diazotized in the usual way and the monocoupled product added to the yellow suspension of the tetrazonium salt. 2N Sodium carbonate was added to raise the pH to 5.0-5.5, stirred for 1 hour at 5- 10⁰C then isolated by salting to 20% w/v to give a blue solid (312g) of formula:

The dye gave navy blue shades on cotton with good all-round fastness properties.

Example 46

To N-p-sulphophenyl-3-carboxy-4(3'-amino-6'-sulpho)phenylhydrazinopyrazalone (48.3g), in water (1 litre), at 0-5⁰C, was added cyanuric chloride (3.3g), the reaction mixture stirred for 2hrs at pH 5, then at 35 ⁰C for 4hrs. 2,4- Diaminobenzenesulphonic acid (10.5g) was added, the pH adjusted to 6 and the temperature raised to 7O ⁰C for 12 hrs. On cooling to 0-5⁰C, a suspension of the diazonium salt of p-aminophenyl-β-sulphatoethylsulphone (14.1g), prepared in the usual way, was added and stirring continued until the coupling reaction was complete. The addition of sodium chloride (20% w/v) gave the desired product (92g) as an orange solid of structure:

The dye gave yellow shades on cotton with good all-round fastness properties. Example 47

As described for Example 46 above, but using N-p-sulphophenyl-3-carboxy-4(4'- amino-6'-sulpho)phenylhydrazinopyrazalone. The dye gave reddish yellow shades on cotton with good all-round fastness properties.

Example 48

To N-p-sulphophenyl-3-carboxy-4-(3'-amino-6'-sulpho)phenylhydrazino- pyrazalone (24.2g), in water (1 litre), at 0-5⁰C, was added cyanuric chloride (3.3g), the reaction mixture stirred for 2hrs at pH 5. 2,4-Diaminobenzene- sulphonic acid (21 g) was added, the pH adjusted to 6 and the temperature to 35 ⁰C for 4hrs., and finally to 70⁰C for 10 hrs. On cooling to 0-5⁰C, a suspension of the diazonium salt of p-aminophenyl-β-sulphatoethylsulphone (28.2g), prepared in the usual way, was added and stirring continued until the coupling reaction was complete. The addition of sodium chloride (15% w/v) gave the desired product (71g) as an orange solid of structure:

The dye gave yellow shades on cotton with good all-round fastness properties. Example 49

To 3-methyl-4-(4'8'-disulpho)naphtha-2'-ylazo-aniline (42.1g) ), in water (1 litre), at 0-5⁰C, was added cyanuric chloride (3.3g), the reaction mixture stirred for 2hrs at pH 5, then at 35 ⁰C for 4hrs. 2,4-Diaminobenzenesulphonic acid (10.5g) was added, the pH adjusted to 6 and the temperature raised to 7O ⁰C for 10 hrs. On cooling to 0-5⁰C, a suspension of the diazonium salt of p-aminophenyl-β- sulphatoethylsulphone (14.1g), prepared in the usual way, was added and stirring continued until the coupling reaction was complete. The addition of sodium chloride (20% w/v) gave the desired product (84g) as an orange solid of structure:

The dye gave yellow shades on cotton with good all-round fastness properties. Example 50

To N-p-aminophenyl-3-carboxypyrazalone (21.9g) in water (1 litre), at 0-5⁰C, was added cyanuric chloride (6.5g), the reaction mixture stirred for 2hrs at pH 5, then at 35⁰C for 4hrs and finally at 70⁰C for 10hrs. The reaction mixture was cooled to 0-5⁰C and a suspension of the diazonium salt of p-aminophenyl-β- sulphatoethylsulphone (28.7g), prepared in the usual way, added and stirring continued until the coupling reaction was complete. The addition of sodium chloride (15% w/v) gave the desired product (84g) as an orange solid of structure:

The dye gave yellow shades on cotton with good all-round fastness properties. Example 51

To m-phenylenediaminesulphonic acid (21g) in water (1 litre), at 0-5⁰C, was added cyanuric chloride (6.5g), the reaction mixture stirred for 2hrs at pH 5, then at 35⁰C for 4hrs and finally at 70⁰C for 10hrs. The resultant reaction mixture was cooled to 0-5⁰C, daizotised in the usual way and added to a solution of N-p-(β- sulphatoethylsulphonyl)phenyl-3-carboxypyrazalone (39.2g) and stirring continued until the coupling reaction was complete. The addition of sodium chloride (20% w/v) gave the desired product (79g) as an orange solid of structure:

Application of the dye to cotton under neutral conditions at 130 ⁰C gave yellow shades with good all-round fastness properties.

Example 52

As for example 51, but with p-phenylenediaminesulphonic acid in place of m- phenylenediaminesulphonic acid.

Example 53

To m-phenylenediaminesuiphonic acid (10.5g) in water (1 litre), at 0-5⁰C, was added cyanuric chloride (6.5g), the reaction mixture stirred for 2hrs at pH 5, then at 35 ⁰C for 4hrs. N- β-Aminoethyl-3-carbonamido-6-hydroxy-4-methyl-pyridin-2- one (7g) was added, the pH raised to 8.5 and the temperature to 70 ⁰C. The reaction was continued for a further 8hrs. A suspension of the diazonium salt of p-aminophenyl-β-suiphatoethylsulphone (28.7g), prepared in the usual way, was added and stirring continued until the coupling reaction was complete. The addition of sodium chloride (15% w/v) gave the desired product (92g) as an orange solid of structure:

The dye gave yellow shades on cotton with good all-round fastness properties.

Claims

1. A compound having the formula

where: each of R-i, R2, R3 is H or an alkyl group; X is nitrogen or C-B where B is H, Cl or a methyl group; D and D1 are organic residues, which may be the same or different; and E is an organic residue or a group of the formula

(Formula 2) where R₄, R₅ are each hydrogen, methyl, methoxyl or SO3H.

2. The compound of claim 1, in which the organic residues D, D1 and E are the same.

3. The compound of claimi , in which the organic residues D, D1 and E are different.

4. The compound of any one of claims 1 to 3, in which the organic residues D, D1 and E are residues of monoazo, disazo, anthraquinone, triphendioxazine, formazan or metal phthalocyanine dyes.

5. The compound of any one of claims 1 to 4, in which 'B' is H, Cl, methyl and substituted.

6. The compound of any one of claims 1 to 5, in which any two or all three of R-I, R2, R3 are similar.

7. The compound of any one of claims 1 to 6, in which ¹E' is the residue of a monoazo dye and at least one of D, D1 and E contain a fibre reactive group Z.

8. The compound of any one of claims 1 to 7, in which 'Z' is -SO₂-Y.

9. The compound of any one of claims 1 to 7, in which ¹Z is -NHCO(CH₂)_a- SO₂-Y.

10. The compound of any one of claims 1 to 7, in which 'Z' is -CONH(CH2)t_>- SO₂-Y.

11. The compound of any one of claims 1 to 7, in which ¹Z' is - CONHCH₂CH₂OCH₂CH₂-SO₂-Y.

12. The compound of any one of claims 1 to 7, in which 'Z' is -NHCOCH(hal)CH₂hal.

13. The compound of any one of claims 1 to 7, in which 'Z' is - NHCOC(hal)=CH₂.

14. The compound of any one of claims 1 to 13, in which 'hal' is selected from Cl and Br.

15. The compound of any one of claims 1 to 14, in which 'a' is 2, 3 or 4.

16. The compound of any one of claims 1 to 15, in which 'b' is 2, 3 or 4.

17. The compound of any one of claims 1 to 16, in which Υ is vinyl.

18. The compound of any one of claims 1 to 7, in which Υ is a radical - CH₂CH₂-U, where U is a group removable under alkaline conditions.

19. The compound of any one of claims 1 to 18, in which ¹E' is a group of formula 2 and at least one of D and D1 contains a fibre reactive group Z.

20. The compound of any one of claims 1 to 9, in which 'Z¹ is -SO₂-Y or NHCO(CH₂)_a-SO₂-Y.

21. The compound of any one of claims 1 to 7, in which Ri and R₂ are selected from the group hydrogen, methyl, methoxyl and SO₃H.

22. A compound according to any one of claims 1 to 21, when used for colouring materials.

23. A compound according to claim 22, when used for colouring fibre materials.

24. A compound according to claim 23, when used for colouring natural or regenerated cellulosic materials.

25. A compound according to any one of claims 1 to 24, when used for dyeing.

26. A compound according to any one of claims 1 to 24, when used for printing.

27. A method for colouring a material comprising applying to the material a compound according to any one of claims 1 to 26.

28. A method for colouring both cellulosic and polyester fibres simultaneously comprising applying a reactive dye according to any one of claims 1 to 26 together with a disperse dye.

29. A method for making a compound according to any one of claims 1 to 26, comprising the steps of: reacting 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid with cyanuric chloride (reaction 1 ); reacting the reaction product of reaction 1 with 2.4- diaminobenzenesulphonic acid (reaction 2); and adding to the reaction product of reaction 2 a diazonium salt.