FR2685342A1 - NOVEL DISAZOUIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS REACTIVE DYES. - Google Patents

Abstract

The subject of the invention is the compounds of formula I (CF DRAWING IN BOPI) in which the symbols have various meanings. These compounds can be used as reactive dyes for dyeing and printing organic substrates containing hydroxy groups or nitrogen.

Description

The subject of the present invention is new disazo compounds, their

preparation and their

  use as reactive dyes.

  The invention relates in particular to the compounds of formula I

H 2 NOH R

D-N = N> N = N

4 SO 3 H NR 2-Z

SO 3 H H NR-

  And their salts, as well as mixtures of these compounds or their salts, in which formula D

(CH 2) NR 4-Q

  (b) R 1 and R 3 R 2 and R 4 Q signify, independently of one another, hydrogen, -COOH or -SO 3 H, signify, independently of each other, hydrogen or a C 1 -C 4 alkyl or C 2 -C 4 hydroxyalkyl group, means a fiber-reactive heterocyclic group or a -COCHY 2 -CH 2 Y 1 -COCY 2 = CH 2 group or - COCH 2 Y 1, where Y 1 is chlorine, bromine, -OSO 3 H or -SSO 3 H, and Y 2 is hydrogen, chlorine or bromine, -Q (a) m is 1 or 2, n is 0, 1 or 2, and Z stands for HF

  each azo group being attached to the rest disulfide

  naphthyl in the ortho position of the amino or hydroxy group.

  In the present application, the alkyl and alkoxy groups may be linear or branched, unless otherwise indicated. In the hydroxy-substituted alkyl groups attached to a nitrogen atom, the hydroxy group is preferably located on a carbon atom other than that linked directly to

this nitrogen atom.

  In the remainder of the 1-amino-8-hydroxynaphthalene of the compounds of the formula I, the sulpho group whose position is not determined is preferably located

in position 3.

  R 1 preferably means Rla, Rla means

  fiant -COOH or -503 H R 1 means more preferably

-503 H.

  R 2 preferably means R 2 a, R 2 a means

  hydrogen, methyl, ethyl or 2-hydroxyethyl, in particular R 2 b, where R 2 b is hydrogen or methyl or ethyl, and

especially hydrogen.

  R 3 preferably means R 3 a, R 3 has

  relying on hydrogen or -503 H, especially -503 H.

  R 4 is preferably R 4 a, R 4 is

  using hydrogen, methyl, ethyl or 2-hydroxyethyl, in particular R 4 b, R 4 b being hydrogen or methyl or ethyl,

especially hydrogen.

  Q as a fiber-reactive heterocyclic group preferably means a pyrimidinyl or triazinyl residue containing a labile halogen atom, preferably a chlorine or fluorine atom, especially a (c) z 'Yr T (c) moiety. A- Yc T is = C or = N-, Yc is H, F, Cl, -CN, -CHO, -SR 5, -SOR 5, -SO 2 R 5 or -502 F, Z 1 is H, F, C 1, Br, -NR 6 R 7 or -OR 5, Z 2 means F, C 1, Br or -N COR 8 As-) means a non-chromophoric anion, R 5 is hydrogen or an alkyl group C 1 -C 4, C 1 -C 4 hydroxyalkyl, phenyl or phenyl monosubstituted with a carboxy or sulfo group, R 6 and R 7 signify, independently of one another, hydrogen; a C 1 -C 4 alkyl group, a C 2 -C 4 hydroxyalkyl group; a phenyl group optionally monosubstituted with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, sulfo or carboxy group; C 1 -C 3 (phenyl) -alkyl optionally monosubstituted in the phenyl ring by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, sulfo or carboxy; a group - (CH 2) t -SO 2 -X, -CH 2 CH 2 -O (CH 2) t -SO 2 -X or 502-X ot means 2 or 3, X is -CH = CH 2 or - CH 2 CH 2 -Y, Y is hydroxy or a residue which can be cleaved under alkaline conditions, for example -OSO 3 H, C 1, Br,

  -OPO 3 H 2, -SSO 3 H, -OCOCH 3, -OCOC 6 H 5 OR

  -O 502 CH 3, or -NR 6 R 7 is a piperidine, piperazine, N-methyl-piperazine or morpholine ring, and R 8 is hydroxy, -NH 2, methoxy or ethoxy. A preferably means a chloride ion,

acetate or methylsulfate.

  Y as a residue which can be cleaved under alkaline conditions, preferably means Cl, -OSO 3 H, or -SSO 3 H, especially -OSO 3 H. X preferably means Xa, Xa signifying -CH = CH 2, -CH 2 CH 20 H or - CH 2 CH 20 SO 3 H, in particular Xb, Xb meaning -CH = CH 2 or -CH 2 CH 2 OSO 3 H, and especially Xc ,, Xc signifying -CH 2 CH 2 OSO H. The remainder (c) preferably means a residue (c 1) or (c 2), o Z 1 t R 6 a and R 11 -NR 6 a R 7 a (c 1) (c 2) means C 1 , -O-C 1 -C 2 alkyl or -NR 6 R 7 a, signify, independently of one another,

  hydrogen, methyl, ethyl, 2-hydroxy-

  ethyl, phenyl optionally monosubstituted with methyl, methoxy, sulfo or carboxy, - (CH 2) t -SO 2 -Xa OR -CH 2 CH 2 -O- (CH 2) t -SO 2Xa or signifies a piperidine ring or morpholine, Z 'Z 2' means F or Cl, Yc 'means hydrogen, Cl, -CN, -CHO or

-SO 2 CH 3,

  Z 1 "means hydrogen, F or Cl, and

Z 2 "means F or CI.

  As remainder (c 1) or (c 2), there may be mentioned in particular the following remains:

N CH 2 O

NHICH 2 CH 2 OH

1 <NR (CH 2) t 502-Xc

N ,, 2

  N N = NH 2 Z 'N 2 N O 2 NHCH 2 CH 2 -O (CH 2) t -502-XC Zy

_ 3, <2

CH 2 NC

I -

CH 2 CH 3

  Z 1 or O 2, wherein each Z 2 ', t and Xc are as defined above or C 1 H 4 C F H F N H NH H F or N Yc O Uc l C 1

  o Yc 'is as defined above.

  (c 1) preferably means a remainder (ci '),

  (c 1 ') signifying the remainder (c 1) in which Z 1' signifies

  C1 or -NR 6 to R 7 a and (c 2) preferably means a residue (c 2 '), (c 2') signifying the remainder (c 2) in which Yc 'signifies hydrogen, Cl or - CN and Z "1 'means F

or Cl.

  Q is preferably Qa, Qa is a residue (c), -COCHY 2 -CH 2 Y 1 or -COCHY 2 = CH 2, in particular Qb, Qb is a residue (c 1) or (c 2), more particularly Qc, Qc meaning a remainder (c 1 ') or (c 2'), and especially Qd, Qd meaning a remainder

(c 2 ').

  The remainder (a) preferably means a residue (a,), R 3/5 4 b NR 4 b -Qb (a,) o -NR 4 b Qb is located in position 4 or 5, in particular a residue (a 2) SO H 503 H 4 A / 'o -NH-Qc is located at position 4 or Q 5, 4 Qc 5 (a 2) and especially a remainder (a 3), (a 3) signifying the remainder

(a 2) wherein Qc means Qd.

  The remainder (b) preferably means a restaurant),

(SQ H)

  Wherein X is O or 1, (CH 2) n NH Qb (b 1), in particular a remainder (b 2), (b 2) signifying the remainder (b 1) in which Qb signifies Qc and the positions are as follows: (i) n 'means 1, -CH 2 -NH-Qc is located in position; m is 1 and the sulfo group is in position 1, (ii) n 'is 1, -CH 2 -NH-Qc is in position; m is 2 and the sulfo groups are in position 1 and 7, (iii) n is 0, -NH-QC is in position 6; m is 2 and the sulfo groups are located in position 4 and 8, and especially a rete (b 3), (b 3) meaning the remainder

(b 2) wherein QC means Qd.

  D preferably denotes D 1, D 1 signifying a residue (a 1) or (b 1), in particular D 2, D 2 signifying a residue (a 2) or (b 3), more particularly D 3, D 3 signifying a remainder (a 2), and especially D 4, D 4

meaning a remainder (a 3).

  The preferred compounds of formula I are those having the formula Ia H N OH Ra 2 Rl

D 2N = N N = N

  Ia s 03 & R and their salts, wherein D 2, R 1, R 2b and Z are as defined above and each azo group is located at the ortho position of the amino group or

  hydroxy on the remaining disulfonaphthyl.

  Particularly preferred compounds are those of formula Ib

H 2 NOH SO 3 H

D 3 -N = N N = N 4

  503 H 503 H H N 2 b Z Ib and their salts, in which formula D 3, R 2 b and Z are as defined above and o -NR 2 b-Z is located in

position 4 or 5.

  Especially preferred compounds are those of formula Ib o (1) R 2 b is hydrogen, (2) those of (1) o -NH-Z is at position 5,

  (3) those of (1) or (2), where D 3 is D 4.

  When a compound of formula I is in the salt form, the cation of the sulfo groups and any carboxy group is not critical and may be any of the non-chromophore cations usually present in the reactive dyes,

  provided that the corresponding salts are hydro-

  As examples of such cations, mention may be made of alkali metal cations and the optionally substituted ammonium cation, for example cations.

  lithium, sodium, potassium, ammonium, mono-, di-, tri-

  and tetramethylammonium, tri-ethylammonium and mono-, di-

and tri-ethanolammonium.

  The preferred cations are the alkali metal cations and the ammonium cation, the sodium cation

  being particularly preferred.

  In the compounds of formula I, the cations of the sulfo and carboxy groups may be identical; they may also be different, for example a mixture of the above-mentioned cations, the compounds of formula I being in the form of mixed salts. The invention also relates to a process for the preparation of the compounds of formula I or mixtures thereof, the process according to which 3,6-4,6,6,6-disulphonic lamino-8-hydroxynaphthalene acid is reacted with the diazonium salt of an amine of formula II

D-NH 2 (II)

  D is as defined above, and on the other hand with the diazonium salt of an amine of formula III R 1

H 2 N 'III

NR -Z

  R 1, R 2 and Z are as defined above.

  The two coupling reactions can be carried out according to the usual methods. Preferably, the coupling on the side of the naphthalenic nucleus is -NH 2 is carried out first using an acidic reaction medium, preferably at pH 2-3. followed by copulation on the kernel side

  naphthalenic acid is fixed in a reaction medium

  neutral to weakly alkaline action, preferably

7.5-9.

  The compounds of formula I can be isolated according to the usual methods, for example by salting out with an alkali metal salt, filtration and drying optionally under vacuum and at temperatures

slightly elevated.

  Depending on the reaction and isolation conditions, the compound of formula I is obtained in the form of a free acid or preferably in salt form or even in the form of a mixed salt containing for example one or more of the indicated cations. previously The free acid can be converted according to the usual methods into salt or mixed salt or vice versa, or a salt into another salt. It should be noted that the group Z 6 N'3-4 HF can take two forms. isomers, the fluorine atom may be in position 2 or 6 Other pyrimidinyl groups indicated as meaning of Q containing substituents whose position is not determined may be in the form of

analogous isomers.

  In general, it is preferred to use this mixture as it is obtained without isolating each of the isomers; however we can, if necessary, separate

  each of the isomers according to the usual methods.

  The starting materials of formulas II and III are known compounds or can be obtained according to

  known methods from known compounds.

  The amines of formula III can for example be obtained by condensation of the compounds of formula IV R 1

H 2 N IV

H NHR 2

  R 1 and R 2 are as defined above, with 2,4,6-trifluoropyrimidine This reaction is advantageously carried out at a temperature of between 0 and 401 ° C. (preferably between 0 ° C. and 201 ° C.) and

a p H between 6 and 9.

  The amines of formula II may be prepared according to a method analogous to that described above, by reaction of a benzene diamine or

  naphthalene with a suitable compound for the introduction

  The compounds of formula I and mixtures thereof can be used as reactive dyes for dyeing or printing organic substrates containing hydroxy groups or nitrogen. The preferred substrates are leather and other materials. wholly or in part, of natural or synthetic polyamides and in particular of natural or regenerated cellulose such as cotton, viscose and fibran. Particularly preferred substrates are

those made of cotton.

  The dyeing or printing is carried out according to the methods usually used in the field of reactive dyes Dyeing with the compounds of formula I is preferably carried out by exhaustion at temperatures between 300 and 801 ° C., in particular between 50 and 600 ° C. .

  The compounds of the invention can easily

  be combined with other known reactive dyes; they may be applied alone or in combination with suitable reactive dyes of the same category having similar dyeing properties, in particular as regards the general fastness and the climbing power on the fiber The dyes obtained with such mixtures have good fastnesses and are comparable to those obtained

with a unique dye.

  The compounds of formula I give

  of exhaustion and high fixation In addition, the

  The dyes and prints obtained with the compounds of the formula I have good fastness to light and wet, especially

  washing, with water, with sea water and with perspiration.

  They are also resistant to oxidation by

  chlorinated water, bleaching

  chlorites and washing baths containing

peroxides or perborate.

  In addition, the dyes and prints obtained with the compounds of formula I exhibit a high resistance to acid hydrolysis, an undyed accompanying fabric being for example only very slightly colored when it is brought into contact with the

  dyed fabric and diluted acetic acid.

  The following examples illustrate the invention without in any way limiting its scope.

  examples, the parts are by weight unless

  otherwise, and temperatures are indicated

in degrees Celsius.

Example 1

  In 1700 parts of water, we suspend

  188 parts of 2,4-diaminobenzenesulphonic acid and dissolved at pH 7 by the addition of a 30% solution of sodium hydroxide.

  drip to p H 7 140 parts of 2,4,6-trifluoro-

  pyrimidine The reaction is carried out at 0 for 3 hours, and then the reaction product is dinitrated with sodium nitrite and hydrochloric acid.

  by following the usual methods.

  To the acid solution of the diazonium salt obtained above, 152 parts of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid (which has been finely ground) are added. The pH of the reaction medium is then gradually raised. first of all, after 2 hours at pH 2.5, by addition of a sodium acetate solution, and then at pH 7.5 by addition of a sodium carbonate solution. the reaction mixture using sodium chloride, the precipitated compound is filtered off and

  it is dried under vacuum at 600. The compound obtained corresponds

  pond, as free acid, to the formula

SO 3 H H 2 NOH SO 3 H

F NH H O SOSH H F

N 3 3

/ H R F

  It dyes the cotton in a dark navy shade. The dyes obtained have excellent fastnesses to

  light and wet and resist oxidation.

  Examples 42: Proceeding as described in Example 1 and using the appropriate starting materials, the compounds of formula I which are indicated in the following table can be prepared. They correspond to formula (A)

3 H N OH R

NS-Q53 R 5 SQ NH-Z (A)

NH-Q SO H 03

  in which the symbols are as defined in

table.

  When the diazotization components are different, especially when Q and Z are different, the coupling reactions must be carried out

  separate steps using an equiva-

  molar of each diazo compound at specific pH

as described in Example 1.

  In the table, Z means H F and Q means Q 1 Q 17, O Q 1 means Z Q 2 means Cl F Q 3 means Q 4 means

Q 5 means -

  Q 6 means Q 7 means C 1 _N? NH 2 C 1

NHCH 2 CH 20 H

C 1

N O <N /

  N __ / O Q 1 o means Qll means Q 12 means F / N N

N = NH 2

FN <

N = NHCH 2 CH 2 OH

  F NO N O C 1 N = 5 Q 8 means Q 9 means Q 13 means NHCH 2 CH 25 00-Xc F

NCH 2 CH 25 2-X

NHCH 2 CH 25 02 XC

C 1 F

  N <14 means CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 O 2 CH 2 O 2 CH 2 O x CH 2 CH 2 O XCH 2 CH 2 O 2 CH 2 O 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C F ci F Ci

CN C 1

  Q 15 means Xi SO 3 H NR H 1 Ci F Q 16 means CH 3 and Q 17 means 3

2 5 -

CAH C 2 H 5

  The compounds of Examples 2 to 42 can be applied to substrates which contain cellulosic fibers, in particular textile materials containing cotton, according to the conventional method.

  by exhaustion dyeing or by the processes of

  usual pressure; The dyes and prints obtained on the cotton have a good fastness to light and color.

  wet and resistant to oxidation.

  TABLE / Position Compounds of Ex.No Q -NH-Q Qi. do. do. do. do. Q 2 do. Q 3 do. do. Q 4 do. Q 5 do. Q 10 o do. Q 6 do. do. Qlli do. Q 7 do. Q 012 do. Q 8 do. do. Q 13 do. formula (A) position

R 3,503 H

  503 H do. do. H 503 H do. do. do. do. H 503 H do. do. do. do. do. H 503 H H 503 H do. H 503 H do. do. H 503 H H H 503 H of R 1 503 H COOH 503 H do. do. do. COOH 503 H do. do. do. do. do. COOH

SO 3 H

  do. do. do. do. do. do. do. do. do. COOH do. 503 H do. do. do. position of -NH-Z TABLE / continued position position position of Ex.No Q -NH-Q R 3 503 H R 1 -NH-Z

32 Q 9 5 503 H 3 503 H 5

  33 do 5 do 3 COOH 5 34 Q 14 5 do 3 503 H 5 do 3 H 3 do 5 36 Q 15 4 H 3 do 5 37 do 3 H 4 do 5 38 do 4 503 H 3 do 5 39 Q 16 3 H 3 do 5 do 4 503 H 4 COOH 5

41 Q 17 4 H 3 SO 3 H 4

  Using the procedure described in Example 1, the compounds of Examples 1-42 are obtained in the form of the sodium salt. By changing the reaction or isolation conditions or by using other conditions. known methods, it is possible to prepare the compounds as free acid or in the form of other salts or even mixed salts which contain one or more of

  cations indicated in the description.

  As stated in the description, the

  compounds of Examples 1 to 42 (and the free acids and other corresponding salts) contain two isomeric compounds because of the group Z 1 2 HF a compound in which the fluorine atom, whose position is not determined, is in position 2 on the pyrimidine ring and the corresponding compound in which the fluorine atom is in position 6, the latter usually predominating. This also applies to the Q group when it means Q 1, Q 2 or Q 4 These isomeric mixtures can be used as such in the usual dyeing or printing processes, without it being necessary to separate the isomers. The following application examples

illustrate the invention.

  Application Example A: 0.3 part of the compound of Example 1 is dissolved in 300 parts of demineralized water and 15 parts of sodium sulfate (calcined) are added. The dyeing bath is heated to 500 and introduced therein. 10 parts of a cotton fabric (bleached) After 30 minutes at 50, 0.2, 0.6, 1.2 and finally 4.0 parts of sodium carbonate are introduced into the bath every 10 minutes ( calcined) During the addition of

  sodium carbonate, the temperature is maintained at 50.

  The dye bath is heated to 600 and the

  dyeing for another 1 hour at 600.

  The fabric is then rinsed with cold water for 3 minutes and then with hot water for 3 minutes. The fabric is boiled for 15 minutes in 500 parts of demineralized water in the presence of 0.25 parts of soap. de Marseille After rinsing with hot water (for 3 minutes) and spinning, the fabric is dried in an oven at about 700. On the cotton is obtained a dyeing of navy blue tint having good fastnesses, in particular high wet fastnesses. and resistant to oxidation. Application Example B: To a dye bath containing 300 parts of demineralized water, 10 parts of sodium sulphate (calcined) and 10 parts of cotton fabric (bleached) are added. The bath is heated to 500 ml. 10 minutes and 0.5 part of the compound of Example 1 is added. After 30 minutes at 500, 3 parts of sodium carbonate (calcined) are added. The dye bath is then heated to 60 and it is continued. 600 dyeing

for another 45 minutes.

  The dyed fabric is rinsed with cold water and then with hot water and washed at the boil according to the method indicated in application example A. After rinsing and drying, a dye is obtained on the cotton of a blue-navy hue having solidities identical to those indicated in application example A. The compounds of Examples 2-42 or their mixtures for dyeing the cotton may also be used according to the method described in application examples A or B The dyes thus obtained on the cotton are of a navy blue shade and have good fastnesses. Application Example C: According to the usual printing methods, a printing paste containing parts of the dye of Example 1, parts of urea, 350 parts of water, 500 parts of dye, is applied to a cotton fabric. a thickener based on 4% sodium alginate, and parts of sodium bicarbonate 1000 parts

  The printed fabric is dried and the

  steam pressure at 102-1040 for 4-8 minutes The fabric is then rinsed with cold water and hot water, washed at the boil (according to the method described in application example A ) and dried. A navy blue print having good fastnesses is obtained. The compounds of Examples 2 to 42 or mixtures thereof can also be used to print the

  according to the method indicated in the application example

  cation C All impressions obtained are blue

  marine and have good solidity.

Claims (1)

Compounds of formula IH 2 NOH R ND-N = N NN / 4 503 H NR 2 -z 503 HHI and their salts, as well as mixtures of these compounds or of their salts, in which formula 3 R 3 (SO 3H) m D means or NR 4 -Q (CH 2) -NRA -Q (a) (b) R 1 and R 3 R 2 and R 4 Q mnz signify, independently of one another, the hydrogen, -COOH or -503 H, signify, independently of one another, hydrogen, C 1 -C 4 alkyl or hydroxy C 2 -C 4 alkyl, signifies a heterocyclic group reactive with the fibers or a group -COCHY 2 -CH 2 Y 1, -COCY 2 = CH 2 or -COCH 2 Y 1, or Y 1 signifies chlorine, bromine, -O 503 H or -S 503 H, and Y 2 means hydrogen, chlorine or bromine, means 1 or 2, means 0, 1 or 2, and means FHF, each azo group being attached to the disulfonaphthyl residue in the ortho position of the amino or hydroxy group. A compound according to claim 1, characterized in that Q as a fiber-reactive heterocyclic group means a pyrimidinyl or triazinyl residue containing a labile halogen atom. A compound according to claim 1 or 2, characterized in that D is a radical of formula (a). A compound according to any one of claims 1 to 3, wherein R 1 is -COOH or -SO 3 H and R 3 is hydrogen or -SO 3 H. A compound according to any of the claims 1 to 4, characterized in that R 2 and R 4, independently of one another, are hydrogen, methyl, ethyl or 2-hydroxyethyl. A compound according to any one of claims 1 to 5, characterized in that Q means a residue (c) Z 2 y T (c) z 1 -COCHY 2 -CH 2 Y 1 or -COCHY 2 = CH 2, o Y 1 is chlorine, bromine, -OSO 3 H or -SSO 3 H, Y 2 is hydrogen, chlorine or bromine, Yc T is = C or = N-, Yc is H, F, C 1 , -CN, -CHO, -SR 5, -SOR 5, -SO 2 R 5 or -SO 2 F, Z 1 means H, F, C 1, Br, -NR 6 R 7 or -OR 5, SIF Z 2 is F, C 1, Br or A, COR 8 AO is a non-chromophore anion, R 5 is hydrogen or C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, phenyl or phenyl monosubstituted by a carboxy or sulfo group, R 6 and R 7 signify, independently of each other, hydrogen; a C 1 -C 4 alkyl group, a C 2 -C 4 hydroxyalkyl group; a phenyl group optionally monosubstituted with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, sulfo or carboxy group; C 1 -C 3 (phenyl) -alkyl optionally monosubstituted in the phenyl ring by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, sulfo or carboxy; a group - (CH 2) t -SO 2 -X, -CH 2 CH 2 -O- (CH 2) t -SO 2 -X or, where t is 2 or 3, X is -CH = CH 2 or - CH 2 CH 2 -Y, Y is hydroxy or a residue which can be cleaved under alkaline conditions, or -NR 6 R 7 is a piperidine, piperazine, N-methyl-piperazine or morpholine ring, and R 8 is hydroxy, -NH 2, methoxy or ethoxy. A compound according to claim 1, wherein it corresponds to the formula Ia H 2 NOH R 2 D 2 -N = NNN to 503 H wherein each azo group is located in the ortho position of the amino or hydroxy group on the disulfonaphthyl residue, Z is as defined in claim 1, Rja is -COOH or -503H, R 2b is hydrogen or methyl or ethyl, D 2 is a residue (a 2) or (b 3) SO H 4 / \ o -NH-QC is located in position 4 or, (a 2) (SO 3 H) m \ 8 1. 7 om means 1 or 2 and 6 n 'means O or 1, (4) (CH 2) 7-NH-Qd (bs) and the positions are as follows: (i) n 'means 1, -CH 2 -NH-Q, is located in position; m is 1 and the sulfo group is in position 1, (ii) n 'is 1, -CH 2 -NH-Q, is in position; m is 2 and the sulfo groups are in position 1 and 7, (iii) n is 0, -NH-QC is in position 6; m is 2 and the sulfo groups are in position 4 and 8, Qc is a remainder (cl ') or (c 2'), and Qd is a remainder (c 2 '), c 1') means a remainder (cl ) and (c 2 ') signifies a residue (c 2) Z 1 NZ 1 z' 2 c 2 (Ci) (c 2) where Z 1 'signifies chlorine or -NR 6 a R 7 a, R 6 a and R 7 a, independently of one another, means hydrogen, methyl, ethyl, 2-hydroxyethyl, phenyl optionally monosubstituted with methyl, methoxy, sulpho or carbonyl, - (CH 2 ) t-SO 2 -Xa or -CH 2 CH 2 -O (CH 2) t -SO 2 -Xa O t is 2 or 3, and Xa is -CH = CH 2, -CH 2 CH 20 OH or -CH 2 CH 2 0503 H or -NR 6 to R 7 a means a piperidine or morpholine ring, Z 2 'means F or Cl, Yc' means hydrogen, Cl or -CN, and each Zii and Z 2 "means F or C 1. 8 A compound according to claim 7, characterized in that it corresponds to the formula Ib H 2 NOH SO 3 HD 3 -N = N NN 4 2 / .NO HNR 'Z Ib in which R 2 b and Z are as defined in the claim n 7, -NR 2 bZ is located in position 4 or 5, and D 3 is a residue (a 2) as defined in claim 7. A compound according to claim 8, characterized in that R 2 b means 'hydrogen. a compound according to claim 9, characterized in that -NH-Z is located in position 5. 11 A process for the preparation of the compounds of formula I as specified in claim 1 or mixtures thereof, characterized in that 1-amino-8-hydroxynaphthalene-3,6 or 4,6-disulfonic acid on the one hand with the diazonium salt of an amine of formula II D-NH 2 (II) where D is as defined in claim 1, and secondly with the diazonium salt of an amine of formula III R 1, R 2, and Z are as defined in claim 1. The use of compounds specified in any one of claims 1 to 10, and mixtures of these compounds, as reactive dyes for dyeing or printing organic substrates containing hydroxy groups or nitrogen. The use according to claim 11, characterized in that the substrate is natural or regenerated cellulose. Organic substrates containing hydroxy groups or nitrogen, characterized in that they have been dyed or printed with a compound as specified in any one of the claims   1 to 10, or a mixture of these compounds.   Materials made of natural or regenerated cellulose, characterized in that they have been dyed or printed with a compound such as   as specified in any one of claims 1 to   , or a mixture of these compounds.