GB2262533A

GB2262533A - Fibre-reactive disazo compounds

Info

Publication number: GB2262533A
Application number: GB9226260A
Authority: GB
Inventors: Markus Gisler; Roland Wald
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1991-12-20
Filing date: 1992-12-16
Publication date: 1993-06-23
Anticipated expiration: 2012-12-16
Also published as: FR2685342B1; CN1056634C; CN1074229A; GB9226260D0; DE4241924A1; KR930013005A; MX9207425A; PT101146A; KR100236804B1; ES2062929A1; JPH06220347A; FR2685342A1; CN1048745C; PT101146B; TR28458A; ES2062929B1; BR9205067A; CH684482A5; CN1090867A; GB2262533B

Description

1'2.1 2 6 2 5 3 3 FIBRE-REACTIVE DISAZO COMPOUNDS This invention relates

to fibre-reactive disazo compounds and a process for their preparation. These compounds are suitable for use as fibre- reactive dyestuffs in any conventional dyeing or printing processes.

More particularly, the invention provides compounds of formula I 1,5N OH R, D-NN 3 N=N 4 S 03H 3H H I and salts thereof, or a mixture of such compounds or salts, in which D is 3 R 3 4 IRC---Q (a) in ,' 3 i (CH2 _n4-Q (b) each of R, and R3 is independently hydrogen, -COOH or -S03H, each of R2 and R4 is independently hydrogen, CI-4alkyl or C2-4hydroxyalkyl, is a heterocyclic fibre-reactive radical or a group -C0C1iY2-CH2Y1, -COCY2=CH2 or -COCH2YI, wherein Yj is chlorine, bromine, -OS03H or -SS035, and Y2 is hydrogen, chlorine or bromine, is I or 2, is 0, 1 or 2, and 0 Z is 'N Y F H F Case 150-5559 with the proviso that each azo radical is bound to a position ortho to the amino or hydroxy group of the disulphonaphthyl radical.

In the specification, any alkyl or alkoxy group present is linear or branched unless indicated otherwise. In any hydroxysubstituted alkyl group which is attached to a nitrogen atom, the hydroxy group is preferably bound to a carbon atom which is not directly attached to this nitrogen atom.

In the 1-amino-8-hydroxynaphthalene radical of compounds of formula I the floating sulpho substituent is preferably in the 3-position.

R, is preferably R,,,, where R,,, is -COOH or -S03H. Most preferably, R, is -S03H R2 is preferably R2a7 where R2a is hydrogen, methyl, ethyl or 2hydroxyethyl. More preferably, R2'is R2by where R2b is hydrogen, methyl or ethyl. Most preferably, R2 is hydrogen.

R3 is preferably R3at where R3a is hydrogen or -S03H, especially -S03H.

R4 is preferably R4a, where R4a is hydrogen, methyl, ethyl or 2hydroxyethyl. More preferably, it is R4by where R4b is hydrogen, methyl or ethyl, especially hydrogen.

Q as a heterocyclic fibre-reactive radical is preferably a pyrimidinyl or triazinyl radical containing a labile halogen substituent, which substituent is more preferably chlorine or fluorine.

More preferably, Q as a heterocyclic fibre-reactive radical is a radical (c), Z2 ' - T Z1 in which Case 150-5559 (c) Y, 1 T i S z;-- C - o r =N-, Y, is H, F, Cl, -CN, -CHO, -SR5, -SOR5, -S02R5 or -S02F, Z1 is H, F, Cl, Br, -NR6R7 or -OR5, Z2 is F, Cl, Br or -etF-, \= AG, COR8 AIP is a non-chromophoric anion, R5 is hydrogen, Cl-4alkyl, Cl- 4hydroxyalkyl, phenyl or phenyl monosubstituted by carboxy or sulpho, each of R6 and R7 is independently hydrogen; Cl-4alkyl, C2-4hydroxyalkyl; phenyl or phenyl monosubstituted by Cl-4alkyl, Cl-4alkoxy, sulpho or carboxy; phenyl(C1-3alkyl) or phenyl(C1-3alkyl) in which the phenyl ring is monosubstituted by Cl-4alkyl, Cl-4alkoxy, sulpho or carboxy; -(CH2)tSO2-X, -CH2CH2-0-(CR2)t-SO2-X or S02-X in which t is 2 or 3, X is -CH=CH2 or -CH2CH2-1, I is hydroxy or a radical which can be split off under alkaline conditions, e.g., -OSO3H, Cl, Br, -OPO3H2, SS03H, -OCOCH3, -OCOC6H5 Or - OSO2CH3, or -NR6R7 is a piperidine, piperazine, N-methyl-piperazine or morpholine ring, and R8 is hydroxy, -NH2, methoxy or ethoxy.

Preferably, AG is a chloride, acetate or methylsulphate ion.

Case 150-5559 Y as a radical which can be split off under alkaline conditions is preferably -OSO3H, Cl or -SS03H, especially -OSO3H.

X is preferably X,,, where X,, is -CHCH29 -CH2CH20H or -CH2CH20SO3H.

More preferably, X is 42 where 4 is -CH=CH2 or -CH2CH20SO3H. Most preferably, it is X,, where X, is CH2CHASO3H, A radical (c) is preferably (c,) or (C2), z 1, N _ N=z, 2 (Cl) zII 1 N Y1 zII c 2 (C2) in which Z1r is Cl, -OCI-2alkyl or -NR6,,R7a, each of R6,, and R7a is independently hydrogen, methyl, ethyl, 2-hydroxyethyl, phenyl, phenyl monosubstituted by methyl, methoxy, sulpho or carboxy, -(CH2)tSO2-Xa or CH2CH2-0-(CR2)t-SO2-Xa, or -NR6aR7a is a piperidine or morpholine ring, Z20 is F or Cl, Y,1 is hydrogen, Cl, -CN, -CHO or S02CH3, Z111 is hydrogen, F or Cl, and Z211 is F or Cl.

Particularly to be mentioned as a radical (c,) or (C2) are the following radicals:

z 1 /1 N - 2 -( N N NH 9 N - /7 N ,, N z 1 NHCH 2 CH 2 OH 3 z 1 N- 2 N= NH (CH 2) t - so 2-Xc Case 150-5559 Z1 Z1 ZT N-, 2 N- 2 N N 3 N NHCH 2 CH 2-0- (CH 2)t- so 2-Xc N 0 ZT Z1 zI N_ 2 2 v N N 3 CH N CH CH CH 3 3 2 3 ZT 2 or N so 3 H in which each Z,', t and X, are as defined above, or N F N cl hT N- F " v "" ' N F)17 _ H F H H F c 1 F H N-\ N- c 1 N c 1 N or F c 1 F c 1 Y 1 c 1 c in which Y,' is as defined above.

3 More preferably, (cl) is (cl'), where (cl') is a radical (cl) in which Z1' is Cl or NR6J7.; and (C2) is (C2% where (c21) is a radical (C2) in which Y.' is hydrogen, Cl or -W and Z1" is F or Cl.

0 is preferably 0,,, where 0,, is a radical (c), -COCHY12-CH2Y1 or COCHY2=CH2. More preferably, Q is QbY where Qb is a radical (cl) or (C2). Even more preferably, Q is Q,, where 0, is a radical (cl') or (C21). Most preferably, Q is Qd, where Qd is (C2t), A radical (a) is preferably (a,), R3 O /5 NR4b-Qb (a,) more preferably, it is (a2), 4 -QC 0- (a2) so 3 H Case 150-5559 in which -NR4b0b is in the 4- or 5-position; in which -NH-Q, is in the 4 or 5-position; most preferably, it is (a3), where (a3) is a radical (a2) in which Qc is ()d A radical (b) is preferably (bl), (SO 3 H) m 8 1 7 6 4 (CH) -,- NH -Q 2 n b in which n, is 0 or 1; (bl) more preferably, it is (b2), where (b2) is a radical (bl) in which Qb is Q,, and the positions are as follows: - (i) n' is 1, CH2NH-Q, is in the 5-position; m is 1 and the sulpho group is in the 1-position; (ii) n' is 1, -CH2-NH-0, is in the 5-position; m is 2 with the sulpho groups in the 1- and 7-positions; (iii) n' is 0, -NH-Qc is in the 6-position; m is 2 and the sulpho groups are in the 4- and 8-positions; Case 150-5559 most preferably, it is (b3), where (b3) is a radical (b2) in which Q. is Qd.

D is preferably D,, where D, is a radical (a,) or (bl). More preferably, D is D2, where D2 is a radical (a2) or (b3); even more preferably, it is D3, where D3 is a radical (a2). Most preferably, D is D4, where D4 is a radical (a3).

Preferred compounds of formula I correspond to formula Ia, H 2 N OH Rla D N= N 2- N=N SO H 1 tR7Z S03H Ia and salts thereof, in which D2, R,,,, R2b and Z are as defined above and in which each azo radical is in a position ortho to the amino or hydroxy group of the disulphonaphthyl radical.

More preferred are compounds of formula Ib, H 2 N OH SO 3 H 4 D3-NI=N N=NNR2-bZ so 3 H so 3H H Ib and salts thereof, in which D3, R2b and Z are as defined above, and in which NR2b-Z is in the 4- or 5position; Most preferred are compounds of formula Ib in which (1) R2b is hydrogen; (2) those of (1) in which -NH-Z is in the 5-position; (3) those of (1) or (2), in which D3 is D4.

When a compound of formula I is in salt form, the cation associated with the sulpho groups and any carboxy group is not critical and may be 8 Case 150-5559 any one of those non-chromophoric cations conventional in the field of fibre-reactive dyes provided that the corresponding salts are water- soluble. Examples of such cations are alkali metal cations and unsubstituted and substituted ammonium cations, e.g., lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetra-methylammonium, triethylammonium and mono-, di- and 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 any 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 invention further provides a process for the preparation of compounds according to formula I or mixtures thereof comprising reacting 1-amino-8-hydroxynaphthalene-3,6 or -4,6-disulphonic acid - on the one hand with the diazonium salt of an amine of formula II, D - NH2 II in which D is as defined above, - and on the other hand with the diazonium salt of an amine of formula III, R H N 2 -?D _NR 2 Z H III in which R,, R2 and Z are as defined above.

Both coupling reactions may be carried out in accordance with conventional methods. Preferably, coupling on the -NH2 side is effected first using an acid reaction medium, preferably at pH 23, followed by coupling on the -OH side in a neutral to weakly alkaline reaction medium, preferably at pH 7.5-9.

The compounds of formula I may be isolated in accordance with known methods, for example, by conventional salting out with alkali metal salt, Case 150-5559 filtering and drying optionally in vacuo and at slightly elevated temperatures.

Depending on the reaction and isolation conditions a compound 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.

It should be noted that the group Z 1 2 N_ 6 N 3 H F can occur in two isomeric forms, with the floating fluorine substituent in either the 2- or the 6-position. Other pyrimidinyl groups indicated as a significance of Q which contain floating substituents can occur in analogous isomeric forms.

In general, it is preferred to use this mixture as it is without resorting to the isolation of a single isomer for use, but should this be desired it can be readily achieved by conventional methods.

The starting compounds of formulae I! and III are either known compounds or may be readily made from known materials using known methods.

Amines of formula III, for example, may be obtained by a condensation reaction of compounds of formula IV, R, H,pN --:

H NHR2 IV in which R, and R2 are as defined above, Case 150-5559 with 2,4,6-trifluoropyrimidine. This reaction is suitably carried out at a temperature of from O'-40'C (preferably 01-20IC) and at a pH of from 6- 9.

Amines of formula II may be prepared in accordance with a method analogous to that above by reacting a benzenic or naphthalenic diamine with a corresponding compound to introduce the radical Q.

The compounds of formula I and mixtures thereof are useful as fibrereactive dyestuffs for dyeing or printing hydroxy group- or nitrogencontaining organic substrates. Preferred substrates are leather and fibre material comprising natural or synthetic polyamides and, particularly, natural or regenerated cellulose such as cotton, viscose and spun rayon. The most preferred substrate is textile material comprising cotton.

Dyeing or printing is effected in accordance with known methods conventional in the fibre-reactive dyestuff field. Preferably, for the compounds of formula I the exhaust dyeing method is used at temperatures within the range of 301 to 801C, particularly at 501601C.

The compounds of this invention have good compatibility with known fibrereactive dyes; they may be applied alone or in combination with appropriate fibre-reactive dyestuffs of the same class having analogous dyeing properties such as common fastness properties and the extent of ability to exhaust from the dyebath onto the fibre. The dyeings obtained with such combination mixtures have good fastness properties and are comparable to those obtained with a single dyestuff.

The compounds of formula I give good exhaust and fixation yields when used as dyestuffs. Moreover, any unfixed compound is easily washed off the substrate. The dyeings and prints derived from the compounds of formula I exhibit good light fastness and good wet fastness properties such as wash, water, sea water and sweat fastness. They also exhibit good resistance to oxidation agents such as chlorinated water, hypochlorite bleach, peroxide bleach and perborate-containing washing detergents.

Case 150-5559 Furthermore, the dyeings and prints obtained with the compounds of formula I show notably high stability to acid hydrolysis, for example, a dyeing when contacted with dilute acetic acid, only shows a slight staining of the undyed accompanying fabric.

The invention is further illustrated with reference to the following nonlimiting examples, in which all parts are expressed by weight unless otherwise stated and all temperatures are in degrees Centigrade.

Example 1

188 Parts of 2,4-diaminobenzenesulphonic acid are suspended in 1700 parts of water and are dissolved at pH 7 by the addition of 30% sodium hydroxide solution. To this solution, 140 parts of 2,4,6- trifluoropyrimidine are added dropwise at pH 7. Reaction is effected at 01 for three hours, afterwards the reaction product is diazotized with sodium nitrite in a hydrochloric acid medium in accordance with a conventional manner.

To the acid diazonium salt solution obtained above, 152 parts of 1-amino8-hydroxynaphthalene-3,6-disulphonic acid (which has been finely ground) are added. The pH of the reaction mixture is then raised stepwise, first within two hours to pH 2.5 by the addition of sodium acetate solution, and then to pH 7.5 by the addition of sodium carbonate solution. Subsequently, the reaction mixture is salted out using sodium chloride, and the dyestuff which precipitates is filtered off and dried at 601 under vacuum. The dyestuff corresponds to the formula (which is in free acid form) so 3 H H 2 N OR so 35 H N=N N=N 2 1-1,'CN NH so 3 H so 3 H N F H _Y H F Case 150-5559 and dyes cotton in deep navy blue tones. These dyeings exhibit excellent fastness properties such as light- and wet-fastness properties and they are resistant to oxidative influences.

Examples 2 - 42 By analogy with the method described in Example 1, using appropriate starting compounds further compounds of formula I may be prepared which are listed in the following Table. They correspond to the formula (A) 3 3 H 2 N OH R 'ON=N 3 1 N--N---- 4 so 3 H so 3 H NH- Q in which the symbols are as defined in the Table.

NH-Z (A) In the case where different diazo component radicals are present, e.g., when Q and Z are different, the coupling reactions have to be carried out in separate steps using an equimolar amount of each single diazo compound at the specific pH as described in Example 1.

In the Table, the entity Z is NI -N H F and Q is Q, - Q17. where 0, is z Q2 is - Cl F H N 'I Q3 is cl F N Q4 is - eN cl cl Q5 i S Q6 N N-111 Q7 is N N-- 08 is - v N) N= Q9 i S 1 N- \ bm 2 cl ;HCH 2 CH 2 OH cl N = % /--.\ N 0 cl NHCH 2 CH 2 so i-xc cl 1. z -, - N NHCH 2 CH 2 OCH 2 CH7SO 2 -X c in which X, is -CH2CHASO3H; Case 150-5559 F S --' N N = NH,? F \ N= NHCH 2 CH 2 OH F N-1 1 Q1 2 i S N N= N 0 N- QI 3 is N F N - Q- 4 is N F KHCH 2 CH 2S027XC MCH,)CH9OCH2CH2S02-xc cl Q, 5 is so 3 H NH- cl 016 i s --/ N CH3 Y N-6 1 - C2H5 Case 150-5559 F and Q17 is CH3 N= N-6 1 -- ';2H5 The compounds of Examples 2 to 42 may be applied to substrates which comprise cellulose fibres, and particularly to textile material comprising cotton using the conventional exhaust dyeing method or conventional printing processes, where dyeings and prints in deep navy blue tones are obtained. These dyeings and prints on cotton show good light- and wetfastness properties and are resistant to oxidative influences.

TABLE Compounds of formula (A) position of position of position of Ex. No. Q NH-Q R3 S03 H R, -NH-Z 2 Q1 5 SO3H 4 SO3H 5 3 do. 5 do. 3 COOH 5 4 do. 4 do. 3 S03H 5 do. 3 H 3 do. 5 6 do. 5 SO3H 4 do. 4 7 02 5 do. 3 do. 5 8 do. 5 do. 4 COOH 4 9 03 5 do. 3 SO3H 5 do. 5 do. 3 do. 4 11 do. 3 H 4 do. 5 12 Q4 5 S03H 3 do. 5 13 do. 5 do. 4 do. 5 14 0 r, 4 do. 3 do. 5 do. 5 do. 4 COOH 4 16 010 5 do. 4 SO3H 4 17 do. 5 do. 3 do. 5 18 Q6 3 H 3 do. 5 19 do. S03H 3 do. 5 do. 3 H 4 do. 5 21 011 5 SO3H 3 do. 5 22 do. 4 do. 4 do. 5 23 07 3 H 3 do. 5 24 do. 5 S03H 3 do. 5 Q12 5 do. 3 do. 5 26 do. 5 do. 4 COOH 5 27 Q8 3 H 3 do. 5 c:

28 do. SO3H 3 S03H 5 29 do. 3 H 4 do. 5 Q13 3 H do. 5 31 do. 5 SO3H 3 do. 5 16 Case 150-5559 TABLE continued position of position of position of Ex.No. Q -NH-Q R3 S03H R, -NH-Z 32 Q9 5 S03H 3 S03H 5 33 do. 5 do. 3 COOH 5 34 Q14 5 do. 3 S03H 5 do. 3 H 3 do. 5 36 015 4 H 3 do. 5 37 do. 3 H 4 do. 5 38 do. 4 S03H 3 do. 5 39 Q16 3 H 3 do. 5 - do. 4 S03H 4 COOH 5 41 Q17 4 H 3 S03H 4 42 do. 5 S03H 3 COOH 4 By the preparation method described in Example 1, the compounds of Examples 1-42 are obtained in their sodium salt form. By changing the reaction or isolation conditions or by using other known methods, it is possible to produce the compounds in the form of free acid or in other salt forms or mixed salt forms which contain one or more of the cations mentioned hereinabove.

As already mentioned hereinbefore in the description, the dyestuffs of Examples 1 to 42 (and the corresponding free acids and other salt forms) contain two isomeric compounds regarding the group Z

1 2 N 6 N 3 H F one compound in which the floating fluorine substituent on the pyrimidine ring is in the 2position and the corresponding compound wherein it is in the 6-position, with the latter usually predominating. The same applies z Case 150-5559 to the group Q present when defined as Q,, Q2 or Q4. These isomeric mixtures may be used in conventional dyeing or printing processes; the isolation of a single isomer for use normally is unnecessary.

In the following examples, the application of compounds of this invention is illustrated.

Application Example A 0.3 Part of the dyestuff of Example 1 is dissolved in 300 parts of demineralised water and 15 parts of Glauber's salt (calcined) are added. The dyebath is heated to 501, then 10 parts of cotton fabric (bleached) are added. After 30 minutes at 500, a total of 6 parts of sodium carbonate (calcined) is added to the bath portionwise every 10 minutes applying quantities of 0.2, 0.6, 1.2 and finally 4.0 parts thereof. During the addition of sodium carbonate the temperature is kept at 501. Subsequently, the dyebath is heated to 60', and dyeing is effected for a further one hour at 601.

The dyed fabric is then rinsed -with running cold water for 3 minutes and afterwards with running hot water for a further 3 minutes. The dyeing is washed at the boil for 15 minutes in 500 parts of demineralised water in the presence of 0.25 part of Marseille soaps. After being rinsed with running hot water (for 3 minutes) and centrifuged, the dyeing is dried in a cabinet dryer at about 700. A navy blue cotton dyeing is obtained showing good fastness properties, and particularly high wet fastness properties, which is stable towards oxidative influences.

Application Example B To a dyebath containing in 300 parts of demineralised water 10 parts of Glauber's salt (calcined), 10 parts of cotton fabric (bleached) are added. The bath is heated to 50 within 10 minutes, and 0.5 part of the dyestuff of Example 1 is added. After a further 30 minutes at 50', 3 parts of sodium carbonate (calcined) are added. The dyebath is then Case 150-5559 heated to 60' and dyeing is continued at 60' for a further 45 minutes.

The dyed fabric is rinsed with running cold and then hot water and washed at the boil according to the method given in Application Example A. After rinsing and drying a navy blue cotton dyeing is obtained which has the same good fastness properties as indicated in Application Example A.

Similarly, the dyestuffs of Examples 2-42 or mixtures of the exemplified dyestuffs may be employed to dye cotton in accordance with the method described in Application Example A or B. The cotton dyeings thus obtained are navy blue and show good fastness properties.

Application Example C A printing paste consisting of parts of the dyestuff of Example 1 100 parts of urea 350 parts of water 500 parts of a 4% sodium alginate thickener and 10 parts of sodium bicarbonate 1000 parts in all is applied to cotton fabric in accordance with conventional printing methods.

The printed fabric is dried and fixed in steam at 102-1041 for 4-8 minutes. It is rinsed in cold and then hot water, washed at the boil (according to the method described in Application Example A) and dried. A navy blue print is obtained which has good general fastness properties Similarly, the dyestuffs of Examples 2 to 42 or mixtures of the exemplified dyestuffs may be employed to print cotton in accordance with the method given in Application Example C. All prints obtained are navy blue and show good fastness properties.

7 19 -

Claims

CLAIMS: -

1. A compound of formula I H2 N OH R, D-N=N 3 4 N=N--- NR-Z so 3 H S03H H I and salts thereof, or a mixture of such compounds or salts, in which (SO 3 H) m i (CH2-NR4-Q (b) D is 3 R3 4 NR4-Q (a) or Case 150-5559 each of R, and R3 is independently hydrogen, -COOH or -S03H, each of R2 and R4 is independently hydrogen, C1-4alkyl or C2-4hydroxyalkyl, Q is a heterocyclic fibre-reactive radical or a group -COCH72-CH2712 - COC72=CH2 or -COCH2'71, wherein Yj is chlorine, bromine, -OS03H or -SS03H, and Y2 is hydrogen, chlorine or bromine, is 1 or 2, is 0, 1 or 2, and Z is N F _ 71< 9 H F with the proviso that each azo radical is bound to a position ortho to the amino or hydroxy group of the disulphonaphthyl radical.

2. A compound according to Claim 1, in which Q as a heterocyclic fibrereactive radical is a pyrimidinyl or triazinyl radical containing a labile halogen substituent.

- 20 Case 1505559

3. A compound according to Claim 1 or 2, in which D is a radical of formula (a).

4. A compound according to any one of Claims 1 to 3, in which R, is Riai where Ria is COOH or S03H, and R3 is R3av where R3a is hydrogen or -S03H

5. A compound according to any one of the preceding Claims 1 to 4, in which R2 is R2a, and R4 is R4., where each Of R2, and R4. is independently hydrogen, methyl, ethyl or 2-hydroxyethyl.

6. A compound according to any one of the preceding Claims 1 to 5, in which Q is Oap where Qa is a radical (c), Z2,Y_ T Z1 (c) -COCHY2-CH2Y1 or -COCHY2=CH2, in which Y, is chlorine, bromine, -OSO3H or -SS03H, Y2 is hydrogen, chlorine or bromine, YC 1 T is -C- or -N-, YC is H, F, Cl, -CN, -CHO, -SR5, SORS, -S02R5 or -S02F, Z1 is H, F, Cl, Br, -NR6R7 or -OR5, 7Z2 is F, Cl, Br or -W \ COR8 Ae is a non-chromoPhoric anion, R5 is hydrogen, Cl-4alkyl, Cl- 4hydroxyalkyl, phenyl or phenyl monosubstituted by carboxy or sulpho, each of R6 and R7 is independently hydrogen; Cl-4alkyl, C2-4hydroxyalkyl; phenyl or phenyl monosubstituted by Cl-4alkyl, Cl4alkoxy, sulpho or carboxy; phenyl(C1-3alkyl) or phenyl(C1-3alkyl) in which the phenyl ring is monosubstituted by Cl-4alkyl, Cl-4alkoxy, -1 sulpho or carboxy; -(CH2)t-SO2-X, Case 150-5559 -CH2CH2-0-(CH2)t-SO2X or in which is 2 or 3, X is -CH=CH2 or -CH2CH2-Y? Y is hydroxy or a radical which can be split off under alkaline conditions, or -NR6R7 is a piperidine, piperazine, N-methyl-piperazine or morpholine ring, and R8 is hydroxy, -NH2, methoxy or ethoxy.

7. A compound according to Claim 1 which corresponds to formula Ia H 2 N OH R1a D,7-N=N N=N S03H so 3 H 1 NRs-Z Ia and salts thereof, in which each azo radical is in a position ortho to the amino or hydroxy group of the disulphonaphthyl radical.

z is as defined in Claim 1, R,,, is -COOH or -S03H.

R2b is hydrogen, methyl or ethyl; is a radical (a2) or (b3), so 3 H 4 1 ' -QC (a2) in which -NH-Q, is in the 4- or 5-position; (SO 3 H) m

8 1 7 6 5 4 (CH A7"H_Qd (b3) in which m is 1 or 2 and n' is 0 or 1, and the positions are as follows:

Case 150-5559 (i) n' 'S 19 -CH2-M-Qd is in the 5-position; m is 1 and the sulpho group is in the 1-position; (ii) n' is 1, -CH2NH-Qd is in the 5position; m is 2 with the sulpho groups in the 1 and 7-positions; (iii) n' is 0, -NH-Qd is in the 6-position; m is 2 and the sulpho groups are in the 4- and 8-positions; Q, is a radical (C11) Or (C21), and Od is a radical (C2t), where (cl') is a radical (cl) and (C2t) is a radical (C2) _N- N= 1 2 (cl) z 1 719 , 1 N Y 1 11 c z 2 (C2) in which Z11 is chlorine or -NR6J7at each of R6,, and R7a is independently hydrogen, methyl, ethyl, 2- hydroxyethyl, phenyl, phenyl monosubstituted by methyl, methoxy, sulpho or carboxy, -(CH2)t-SO2-Xa or -CH2CH2-O(CH2)t-SO2-Xa, in which t is 2 or 3, and Xa is -CH=CH2, -CH2CH20H or -CH2CHAS03H, or -NR6aR7a is a piperidine or morpholine ring, T Z2 ' is F or Cl, Y,' is hydrogen, Cl or -CN, and each of Z1" and Z2" is F or Cl.

Case 150-5559 8. A compound according to Claim 7 which corresponds to formula Ib H.N OH SO H 2 3 D3-N=N N=N- 4 so 3 H so 3 H - NR 2 -b Z H Ib and salts thereof, in which R2b and Z are as defined in Claim 7, and in UR is in the 4- or 5-position, which -1 2b-Z D3 is a radical (a2) which is defined in Claim 7.

9. A compound according to Claim 8, in which R2b is hydrogen.

10. A compound according to Claim 9, in which -NH-Z is in the 5-position.

A compound substantially as hereinbefore described with reference to any one of Examples 1 to 42.

12. A process for the preparation of a compound of formula I as defined in Claim 1, or a mixture of such compounds comprising reacting 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid - on the one hand with the diazonium salt of an amine of formula II, D - N52 II in which D is as defined in Claim 1, - and on the other hand with the diazonium salt of an amine of formula III, R 1 11 1 2 N -:-)NRI-Z H III in which R,, R2 and Z are as defined in Claim 1.

Case 150-5559

13. A process for the preparation of a compound of formula I as defined in Claim 1, substantially as hereinbefore described with reference to any one of Examples 1 to 42.

14. A compound of formula I, whenever obtained by a process according to Claim 12 or 13.

15. A process for dyeing or printing a hydroxy group- or nitrogencontaining organic substrate comprising applying to the substrate a compound according to any one of the preceding Claims 1 to 10 or 14, or a mixture thereof.

16. A process according to Claim 15, wherein the substrate is a fibre material comprising natural or regenerated cellulose.

17. A process for dyeing or printing a substrate substantially as hereinbefore described with reference to any one of Application Examples A to C.

-1