GB2085908A

GB2085908A - Fibre-reactive azo dyestuffs

Info

Publication number: GB2085908A
Application number: GB8130047A
Authority: GB
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1980-10-07
Filing date: 1981-10-05
Publication date: 1982-05-06
Also published as: GB2085908B

Abstract

The present invention relates to asymmetric compounds of formula I, <IMAGE> in which D is the residue of a metal-free azo dyestuff, containing from 2 to 4 sulpho groups and free from fibre-reactive groups, D' has one of the significances of D with the proviso that D and D' are different, each R1, independently, is hydrogen or C1-4alkyl, each of R2 and R3, independently, is hydrogen, C1-4alkyl or 2-, 3- or 4- hydroxyC2-4alkyl, X is a monohydroxy or dihydroxy-substituted straight chain or branched chain C3-10alkylene radical which optionally contains one or two hetero atom-linkages selected from -O- and <IMAGE> or is a C2-10 straight or branched chain alkylene radical. Ra is hydrogen or C1-4alkyl. Hal is fluorine, chlorine or bromine, which compounds are in free acid or salt form, and mixtures thereof, which compounds are useful as fibre- reactive dyestuffs.

Description

SPECIFICATION Improvements in or relating to organic compounds The present invention relates to halotriazinyl-containing compounds, their production and use as fibre-reactive dyestuffs.

More particularly, the present invention provides asymmetric compounds of formula I,

in which D is the residue of a metal-free azo dyestuff, contining from 2 to 4 sulpho groups and free from fibre-reactive groups, D' has one of the significances of D with the proviso that D and D' are different, each R,, independently, is hydrogen or C, 4alkyl.

each of R2 and R3, independently, is hydrogen, C, 4alkyl or 2-, 3- or 4-hydroxyC2 4alkyl, X is a monohydroxy or dihydroxy-substituted straight chain or branched chain C3 10alkylene radical which optionally contains one or two hetero atom-linkages selected from -0- and

or is a C2 10 straight or branched chain alkylene radical, Ra is hydrogen or C, 4alkyi, Hal is fluorine, chlorine or bromine, which compounds are in free acid or salt form, and mixtures thereof.

Examples of residues of monoazo dyestuffs are those which contain components of the aromatic carbocyclic series and heterocyclic series, such as naphthalene, benzene, pyrazolone and pyridone series. Preferred dyestuff residues are of formula Np-N = N-Ar-, Np-N = N-Np-, Ar-N = N-Np and Het-N = N-Ar wherein Np is a radical of the naphthalene series, Ar is a radical of the benzene series and Het is a radical of the heterocyclic series and such residues contain from 2 to 4 sulpho groups.

More preferred residues are those of formula (a), (b), (c), (d), (e), (f) and (g)

in which R4 is hydrogen, C1-4alkyl or C1-4alkoxy, R5 is hydrogen, C1-4alkyl, C1-4alkoxy or -NHCOR6 where R6 is C1-4alkyl, NH2, -NHC1-4alkyl or -N(C1-4alkyl)2, R7 is hydrogen or C1-4alkyl, R8 is hydrogen or C1-4alkyl, R9 is hydrogen or sulpho, R10 is hydrogen, C1-4alkyl, carboxy, phenyl or sulphomethylene; R11 is hydrogen, carboxy, sulpho, sulphomethylene or -CONH2, with the proviso that when R10 is sulphomethylene, R11 is other than sulpho and sulphomethylene; R12 is hydrogen, C1-4alkyl or phenyl;; R13 is hydrogen or sulpho, with the proviso that the radical (e) contains at least two sulpho groups, R14 is C1-4alkyl or carboxy each of R1s and R16, independently, is hydrogen, C1 4alkyl, chlorine or bromine, n is 1 or 2, and m is 0 or 1, with the proviso that the sum of m + n is at least 2, and p is 1 or 2.

The hydroxy-substituted alkylene bridge as X preferably contains from 3 to 6 carbon atoms and is preferably mono-hydroxy-substituted. V\Ihen such alkylene as X contains hetero linkages such as -0- or -N(C1-4alkyl) such hetero linkages are separate4 from the -NR3 and -NR3 groups, the hydroxy groups and from each other by as least two carbon atoms. The unsubstituted alkylene bridge as X preferably contains from 2 to 6 carbon atoms, most preferably 3 carbon atoms.

X is pre-lerably X', where X' is straight chain or branched chain C2 6alkylene or a monohy- droxy-substituted straight or branched chain C3-6alkylene. More preferably X is X", where X" is a monohydroxy-substituted straight or branched chain C3-6alkylene. Most preferably, X is X"', where X"' is

Hal is preferably fluorine or chlorine, more preferably chlorine.

Any alkyl as R1, R2, R3, R4, R5, R6, R7, R8, R1O, R,2, R14, RX5 and R,6 preferably contains 1 or 2 carbon atoms.

Any alkoxy as R4 or R5 preferably contains 1 or 2 carbon atoms and is especially methoxy.

Each Ra, independently, is preferably R'r, where R1' is hydrogen, methyl or ethyl, more preferably R1 is R'1, where R1" is hydrogen or methyl with hydrogen being especially preferred.

Each of R2 and R3, is preferably R'2 and R'3, where each of R2 and R'3, independently, is hydrogen, methyl, ethyl or hydroxyethyl. More preferably R2 and R3 are R'2 and R'3, where each of R'2' and R3", independently, is hydrogen or methyl, with hydrogen being most preferred.

R4 is preferably R'4, where R'4 is hydrogen, methyl or methoxy.

R5 is preferably R'5, where R; is hydrogen, methyl or NHCOR6', where R'e is methyl, ethyl, -N H2, -NHC, 2alkyl or N(C1-2alkyl)2. More preferably R5 is R'5, where R5" is hydrogen, methyl or NHOCR6", where R6" is methyl, ethyl or -N H2, especially methyl or -NH2.

When R5 is -NHCOR6, R4 is preferably hydrogen, and when R5 is C1-4alkyl, especially methyl, R4 is preferably hydrogen or methoxy. When R5 is hydrogen R4 is preferably hydrogen.

R7 is preferably hydrogen.

Re is preferably R'e, where R'e is hydrogen, methyl or ethyl.

R10 is preferably R10', where R'10 is hydrogen or C1-2alkyl, with methyl being most preferred.

R11 is preferably R111, where R11' is hydrogen, sulphomethylene or -CON H2; R12 is preferably R12', where Rl'2 is hydrogen or C1 2alkyl with ethyl being especially preferred.

R13 is hydrogen when R11' is sulphomethylene and is sulpho when R11' is hydrogen or -CONH2.

R14 is preferably R14', where R114 is methyl or carboxy, with carboxy being most preferred.

R15 and R16 are preferably Ri,e and R16', where each of Ri,e and Ri,e, independently, is hydrogen, methyl or chlorine.

p is preferably 1.

In the residues of formula (a) the azo group is bound to the 1 or 2 position, preferably the 2position.

In the radicals of formula (a) when the azo group is bound to the 2-position and when n is 2 and m is 1 the sulpho groups are in the 3,6,8-, 4,6,8-, 1,5,7- or 3,5,7-positions preferably in the 3,6,8- or 4,6,8-positions. When the azo group is the 1-position the sulpho groups are preferably in the 2,5,7- or 3,6,8-positions.

In the radicals of formulae (a) when n is 1 and m is 1 the azo group is preferably in the 2position and the sulpho groups are preferably in the 1,5-,1,6- or 4,8-positions, and when n is 2 and m is 0 they are preferably in the 6,8-positions.

In the radical of formula (d) the azo group is preferably bound to the 2-position and the sulpho groups are preferably in the 1,5- or 1 ,6-positions.

In the radicals of formula (b), (c) and (d) the sulpho groups on the hydroxy-naphthalene are preferably in the 3- and 6-positions.

In the radical of formula (g), preferably the azo group is in the 2-position and the sulpho group in the 1-position.

In the radical of formula (c), preferably one of R8, R9 and the sulpho group is in the 2position, more preferably the sulpho group is in the 2-position.

Preferably only one of D and D' signifies a residue containing a heterocyclic group.

Preferred compounds of formula I are those (i) in which D is a radical of formula (a), in which m is 1 and n is 1 or 2 or, m is 0 and n is 2, R4 is hydrogen and R5 is -NHCOR6, Hal is chlorine, R2 and R3 are R'2 and R'3 and D' is a radical of formula (a), in which m is 1 and n is 1 or 2, R4 is R'4, R5 is R6' other than NHCOR6, and X is X', preferably X".

(ii) in which D is a radical of formula (a), in which m is 1 and n is 2, R2 and R3 are R'2 and R'3, R4 is hydrogen and R5 is -NHCOR6, Hal is chlorine and D' is a radical of formula (a), in which m is 1 and n is 1 and R4 is R'4, R5 is R'5 and X is X', preferably X".

(iii) in which D is a radical formula (a), in which m is 1 and n is 2, R2 and R3 are R2' and R'3, R4 is R4 and R5 is R5, Hal is chlorine, D' is a radical of formula (b) or (c) in which R7 is hydrogen and R8 is R'8, and X is X', preferably X".

(iv) those in which D is a radical of formula (a), in which m is 1 and n is 1 or 2 or, m is O and n is 2, R2 and R3 are R'2 and R'3, R4 is R4 and R5 is R5, Hal is chlorine and D' is a radical of formula (b) or (c), in which R7 is hydrogen and Rs is R'8, and X is X', preferably X".

(v) those in which D is a radical of formula (d), in which R2 and R3 are R'2 and R13, D' is a radical of formula (a), in which n is 1 and m is 1 or n is 2 and m is 0, preferably the latter, R4 is hydrogen and R5 is NHCOR6, Hal is chlorine and X is X', preferably X".

(vi) those in which D is a radical of formula (e), in which R10 is R/10 R11 is R11 and R,2 is R 2, R2 and R3 are R'2 and R'2, D' is a radical of formula (b) or (c), in which R7jS is hydrogen and R8 is R'8, Hal is chlorine and X is X', preferably X".

(vii) those in which D is a radical of formula (f), in which R14 is R't4 and Rt5 is R15, R16 is R'16 and p is 1, R2 and R3 are R: and R3 and D' is a radical of formula (b) or (c), in which R7 is hydrogen and R8 is R'8, Hal is chlorine and X is X', preferably X".

(viii) those in which D is a radical of formula (g) R2 and R3 are R'2 and R'3, D' is a radical of formula (d) or (c) in which Rs is R8, Hal is chlorine and X is X'.

(ix) those of (i) to (viii) in which X is X"'.

(x) those of (i) to (ix) in which R1, R2 and R3 are hydrogen.

The cations of the sulpho groups when the compounds of formula I are in salt form may be any of those non-chromophoric cations common in the chemistry of reactive dyestuffs. Examples of suitable cations are alkali metal cations and substituted or unsubstituted ammonium, such as sodium, lithium, potassium, ammonium, mono-, di- and tetramethylammonium, triethylammonium and mono-, di- and triethanolammonium.

The present invention further provides a process for the production of compounds of formula I, as defined above, comprising condensing a compound of formula ll,

in which F is D or D' with a compound of formula Ill

in which F1 is D' when F is D or is D when F is D'.

The reaction is carried out in accordance with known methods. Suitably the reaction is effected in a neutral to alkaline medium in the presence of an acid binding agent. The reaction temperature is preferably in the range of from 30 to 60 C.

The compounds of formulae ll and Ill may be prepared in accordance with known methods.

The compounds of formula Ill are preferably prepared by reacting the dyestuff F,-NHR1 with 2,4,6-trihalo-1,3,5-riazine, optionally in the presence of an acid binding agent at 0-5 C in a weekly acid medium i.e. pH 4-6.5 and then reacting the product with HNR2-X-NR3H. The second reaction is suitably carried out from room temperature to 50 C in a neutral medium advantageously in the presence of an acid binding agent.

The compounds of formula I and mixtures thereof are useful as reactive dyestuffs for dyeing or printing hydroxy and nitrogen containing organic substrates. Preferred substrates are leather and textiles comprising or consisting of natural or synthetic polyamides such as wool, silk and nylon, natural or regenerated cellulose such as cotton, viscose and spun rayon. When Hal is chlorine dyeing may be effected equally well at 80 C as 100 C. When Hal is fluorine the dyestuffs are so called cold dyes, i.e. dyeing is preferably effected at temperatures in the range of between 20 and 40 C. Dyeing is effected in accordance with known methods. Preferably dyeing is effected by the exhaust method.

The dyeings obtained have good wet fastness such as wash, water and sweat fastness, the dyestuffs give good dye yield and are only very slightly affected by salts. Further, the dyes have good fastness to chlorine and peroxide bleaches.

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

Example 1 191.5 Parts 2-aminonaphthalene-3,6.8-trisulphonic acid are suspended in 500 parts water.

After the addition of 1 25 parts 30% hydrochloric acid with the addition of ice to cool to O to 6 , diazotization is carried out over a period of 45 minutes with 1 25 parts 4 N sodium nitrite solution. Stirring is effected for 1 hour and excess nitrite is decomposed with aminosulphonic acid.

75.5 Parts 1-amino-3-ureidobenzene are dissolved in 250 parts water with the addition of 50 parts 30% hydrochloric acid and cooling to a temperature under 5" with ice. The diazo suspension obtained as described above is slowly added thereto with simultaneously addition of 100parts sodium acetate (crystalline), portionwise. The solution is stirred overnight and then adjusted to pH 4.5 with a little 20% soda solution and salted out with approximately 10 mol % sodium chloride. The dye is filtered off.

At approximately 2", 50 parts cyanuric chloride are added to a solution of the dyestuff so obtained in 800 parts water, the pH of which solution being adjusted to 5 to 5.5. Stirring is effected at a temperature not exceeding 5 . Subsequently, 42 parts cyanuric chloride are added, the pH is adjusted to approximately 5.5 with sodium carbonate solution. After completion of the condensation the reaction mixture is treated with activated charcoal and then filtered clear.

37 Parts 1 ,3-diaminopropanol-2 in 600 parts water are added to the so-obtained dyestuff solution which is stirred overnight at room temperature, the mixture is adjusted to pH 7 and the whole is stirred at 30-40"C for approximately further 6 hours. The product is salted out with sodium chloride and filtered.

Meanwhile 285 parts of the trisodium salt of 8-amino-1-hydroxy-2-(2'-sulphophenylazo)na phthalene-3,6-disulphonic acid in 800 parts water is reacted with 92 parts cyanuric chloride at 0-5". The pH of the solution is adjusted to 4 to 4.5 by the addition of aqueous sodium carbonate solution.

The product obtained thereby is reacted with the condensation product with 1,3-diaminopropanol-2 obtained as described above by stirring at room temperature overnight followed by stirring for approximately 6 hours at a temperature of from 40 to 50"C, the pH having being adjusted to 7. After salting out with sodium chloride, filtering and drying in vacuo at approximately 80 a dyestuff of formula

is obtained, which dyes natural and regenerated cellulose in scarlet shades.

Example 2 6.9 Parts dichlorotriazine monozo dyestuff obtained by acid coupling of diazotized 2 aminonaphthalene-3.6,8-trisulphonic acid with m-aminophenylurea and subsequent condensation with cyanuric chloride are dissolved in 70 parts water and made neutral and reacted at room temperature with a solution consisting of 0.8 parts 1,2-diamino-propane in 8 parts water and 2 parts 30% hydrochloric acid. The mixture is reacted for 5 hours at a pH of 7 to 8 a temperature of 25-35"C. The pH value is maintained by the addition of c. 1 part calcined soda dissolved in a little water. After the reaction is ended the completely-formed precipitated amino dye is filtered to separate out the side-products.The presscake is stirred into 70 parts water at room temperature and then combined with the aqueous solution of approximately 70 parts by volume containing 5 parts of the dyestuff obtained as follows: 4 Parts of the dye obtained by acid coupling of diazotized 2-aminonaphthalene-4,8disulphonic acid with 2-amino-1-methoxy-4-methylbenzene are dissolved in 50 parts water and made neutral and then reacted with 1.8 parts cyanuric chloride with vigorous stirring, the pH of approximately 5 at 20 to 25"C is maintained by the addition of aqueous soda solution. After completion of the reaction the solid colourless impurities are filtered off whereby the solution is ready for use.The connection of the two monoazo dyes is effected over 5 hours at 20 to 30"C whereby the pH is held at 11 to 11,5 by continuous addition of sodium hydroxide solution.

After completion of the reaction in a neutral pH medium the disazo dyestuff is precipitated with the help of sodium chloride and is then filtered. After drying and grinding an orange powder is obtained which dyes cotton and regenerated cellulose fibres in lively golden-yellow shades. The product, in free acid form, is of formula

In analogy with the procedure described in Examples 1 and 2 further dyestuffs, given in the following Table, may be prepared. The dyestuffs are obtained in the sodium salt form. However, they may be converted to other salt forms in accordance with known methods. In Examples 3 to 19, R2 and R3 are hydrogen. In Examples 20 to 52, Hal is chlorine.

T A B L E

8 D 8 8 8 No. cellulose N I, sO3H Oa! 4 do. do. %%oNN%%oNH do. do.

a!3 so 55 f 5 v do. 4 N=N- 4 = %9 3H a a 6 MsoOso r: Q do. so! O N"N do. do.

3 -IN OH Ca!3 7 00N-N do.

c13 - 3H 8 00N.NQNH- do. so3i 003H 0 so3 do. do.

Z 4 ok 4 do. do.

3 sO3H so3H > 3 Z Table continued

6 4 D - 11R1 Hal - NR1 4'e shade on No. 803H NHOH so3H cellulose 9 ;N=Nt Cl N N:N x 8 * 8 t 8 50311 do. ldcnyellow zv 503H N! 1C011112 503H 3 11 do. F do. do. do.

12 do. do. do. 2a!2CHcH2CH2- do.

OH E 13 do. do. do. t-a!2 do.

50311 c,s3 :e u 8 50311 MIcoNH2 OH 503H - OH 15 oo Q- do. o. starlet 4 8 SO3H E Table continued

Ei Easple D a o N SO H 3 X- 3=NHH Cl H0ON=N T 8 0000 11C0NH2 22 scarlet Z N 803H 503T1 a!3 NH- OH tzm N=N Cl 0 0 do. do.

0 8 503H N 50H 3 C2H5 0 NH a!3 n 18 U 5011 b Ci U 3 C2115 H m Uk NH- Cl do. do. do.

Z N t O 2 m E n tD > as

o jR n o o o o o No. D - NRi - - NR1 - --X-N1- dye shade on Ex. H2 R3 cellulose 3H3 503H N:N = 20 zt Is HN 8 S 8 - N 3112 21 do. 3y̆30=N$ do. do.

22 311 - 2a!2a!2H- do.

0 0 3 1150311 t 3H 3 23 do. do. -NHCH2CH2NH- do.

24 do. do. -N12a!2-NH- do.

CH2a!2OH 25 3H=0 do. NH-CH2Wi{2NH do.

tZ1 k g Z NO N NN N N N

8 &commat; d ' 8 " d N -a x Q 8 8 8 I o - &commat; 27 do. do. do.

3 28 do. wWNH do. do.

3 50311 29 do. do. do.

50311 3H mem z4Z F qO)3t, { iz) > & 8 a s 4 Z N N N N f

.f W | ., I f S o d o o e 8 R za 8 8 Sy, Xn ExNo. fl - NR - - NRi - - N - X - N - dye shade on 12' R'3 8 31 H 3H I 3H 3000 -- (a!2) 6 scarlet 32 do. do. -(a!2)3-NH- do.

50 11 50 11 3 3 33 0 0=0 00= -NHa!2a!2-NH- reddish-yellow 3113H 311 OH 34 do. )0o do. do.

50311 3 35 do. (K3H=NmNaO do. do.

I I n CEsS X oi . N .f v ulf f O W Z r n .f Mf rs

Ex. D - - - - N - X - N - dye slade on No. NRi NR1 I cellulose 1212 fg o rf A o z-gf g %N=NT & NH- -NH2CH2-NH - reddish-yellow 3 x 311 o 50 11 50 H 38 do. M0ND03 do. do.

39 do. 1?3H=Nm;}t0 do. do.

50311 40 do. 00N-N do. do.

51 50311 50311N 50311 N=N 41 0000 0000 do bluieb-red 3T1 50311 50311 503H 50311 50311 H 42 do. 0000 do. do.

Ho 11 3 3 311 b a O f N % i ,f tf mf v v v

| o of s D - - NRi - - NR2 - X - NR3- dye shade on cellulose 50 11 - HC-N 43 N 0 . N- ap, S 8 8 F CH2a!2 u/ E, > ) 50311 3 3 45 do.

do. -NHCH2CH2a! do.

46 do. do. -NH2-NH a!3 f 0 . & W m m 48 do. do. 2a!2N,- do.

c112a!2OH i. , i X W.E 3 3 3

.E 8 | 8N x C 8 ( I P s s 50311 50311 CH2CN2OH Z uz S i = v L 52 > 5 < n rs a z 8 8 1 z " r Application Example 1 Part of the dye of Example 1 is dissolved in 300 parts water. 10 parts cotton are added to the dyebath and the temperature is raised to 80 in 10 minutes. 1 5 parts Glauber salts are added and 30 minutes thereafter, 3 parts sodium carbonate. Dyeing is continued for 1 hour.

Subsequently, the dyed material is rinsed cold and then hot. The dyeing is soaped at the boil for 20 minutes in 500 parts water and 0.5 parts sodiumalkylsulphonate. After rinsing a scarlet red dyeing with good light-, wet-, and chlorine-fastness is obtained.

Claims

1. A compound of formula I,

in which D is the residue of a metal-free azo dyestuff, containing from 2 to 4 sulpho groups, and free from fibre reactive groups, D' has one of the significances of D with the proviso that D and D' are different, each R1, independently, is hydrogen or C,4alkyl, each of R2 and R3, independently, is hydrogen, C, 4alkyl or 2-, 3- or 4-hydroxyC24alkyl, X is a monohydroxy or dihydroxy-substituted straight chain or branched chain C3,0alkylene radical which optionally contains one or two hetero atom-linkages selected from -0- and

or is C2,0 straight or branched chain alkylene radical.

Hal is fluorine, chlorine or bromine, Ra is hydrogen or C, 4alkyl, which compounds are in free acid or salt form, and mixtures thereof.

2. A compound according to Claim 1, in which D and D', independently are selected from dyestuff residues of formulae Np-N = N-Ar-, Np-N = N-Np-, Ar-N = N-Np- and Het-N = N-Ar- wherein Np is a radical of the naphthalene series, Ar is a radical of the benzene series and Het is a radical of the heterocyclic series and such dyestuff residues contain from 2 to 4 sulpho groups.

3. A compound according to Claim 2, in which any heterocyclic radical is of the pyrazolone or hydroxypyridone series.

4. A compound according to Claim 1 or Claim 2, in which D and D', independently, are selected from residues of formulae (a), (b), (c), (d), (e), (f) and (g),

IR4 N=NOR4 (a) R5 (SO3H) (SO3H)m (S038)n (503H) m R7 OH (b) S03H S03H R 8 OH H035 4 FN=N X (e) R9 503H S03H N=N OH MM S03H 503H S03H SO3H R1 l$yN=NM::YoRl3 (e) O , OH 503H Rl4N=N (f) OH )T(so3H)p R15 R16 OH I ~I < 503H S03H in which R4 is hydrogen, C1-4alkyl or C1-4alkoxy, R5 is hydrogen, C1-4alkyl, C1-4alkoxy or -NHCOR6 where R6 is C1-4alkyl, NH2, -NHC1-4alkyl or -N(C1-4alkyl)2, R7 is hydrogen or C1-4alkyl, R8 is hydrogen or C1-4alkyl, R9 is hydrogen or sulpho, R10 is hydrogen, C1-4alkyl, carboxy, phenyl or sulphomethylene; R11 is hydrogen, carboxy, sulpho, sulphomethylene or -CONH2, with the proviso that when R10 is sulphomethylene, R11 is other than sulpho and sulphomethylene; R.2 is hydrogen, C1-4alky or phenyl;; R13 is hydrogen, or sulpho, with the proviso that the radical (e) contains at- least two -sulpho groups, R14 is 1-4alkyl or carboxy each of R,5 and R,6, independently, is hydrogen, C1-4alkyl, chlorine or bromine, n is 1 or 2, and m is 0 or 1, with the proviso that the sum of m + n is at least 2, and p is 1 or 2.

5. A compound according to any one of Claims 1 to 4, in which X is X', where X' is a monhydroxy-substituted straight or branched chain C3-6alkylene or is a straight or branched chain C2 6alkylene.

6. A compound according to any one of Claims 1 to 5, in which each R1 is R', where R: is hydrogen, methyl or ethyl.

7. A compound according to any one of the preceding claims, in which each R2 and R3, independently, is R'2 and R3', where R'2 and R'3 are hydrogen, methyl, ethyl or hydroxyethyl.

8. A compound according to any one of Claims 4 to 7, in which R4 is R14, where R'4 is hydrogen, methyl or methoxy and R5 is R5', where R15 is hydrogen, methyl or NHCOR6', where R'6 is methyl, ethyl, -N H2, -NHC1-2alkyl or -N(C1-2alkyl)2.

9. A compound according to any one of Claims 4 to 8, in which, when R5 is -NHCOR6, R4 is hydrogen, and when R5 is C1-4alkyl, R4 is hydrogen or methoxy and when R5 is hydrogen, R4 is hydrogen.

10. A compound according to any one of Claims 4 to 9, in which R7 is hydrogen.

11. A compound according to any one of Claims 4 to 11, in which R8 is R18, where R'8 is hydrogen, methyl, or ethyl.

12. A compound according to any one of Claims 4 to 11, in which R10 is hydrogen or C1-2alkyl, R11 is hydrogen, sulphomethylene or -CONH2 and R13 is hydrogen when R11 is sulphomethylene and is sulpho when R11 is hydrogen or -CON H2.

13. A compound according to any one of Claims 4 to 12, in which R14 is methyl or carboxy, each of R,5 and R,6, independently, is hydrogen, methyl or chlorine and p is 1.

14. A compound according to any one of claims 4 to 1 3, in which D is a radical of formula (a), in which m is 1 and n is 1 or 2 or m is 0 and n is 2, R4 is hydrogen and R5 is -NHCOR6, Hal is chlorine, R2 and R3 are R'2 and R'3 and D' is a radical of formula (a), in which m is 1 and n is 1 or 2, R4 is R'4 R5 is R's other than -NHCOR6, and X is X'.

15. A compound according to any one of Claims 4 to 13, in which D is a radical of formula (a), in which m is 1 and n is 2, R2 and R3 are R'2 and R3', R4 is hydrogen and R5 is -NHCOR6, Hal is chlorine and D' is a radical of formula (a), in which m is 1 and n is 1 and R4 is R4', R5 is R's and X is X'.

16. A compound according to any one of Claims 4 to 13, in which D is a radical of formula (a), in which m is 1 and n is 2, R2 and R3 are R'2 and R3', R4 is R4 and R5 is R5', Hal is chlorine, D' is a radical of formula (b) or (c) in which R7 is hydrogen and R8 is P'8, and X is X'.

17. A compound according to any one of Claims 4 to 13, in which D is a radical of formula (a), in which m is 1 and n is 1 or 2 or m is 0 and n is 2, R2 and R3 are R'2 and R3', R4 is R'4 and R5 is R5', Hal is chlorine and D' is a radical of formula (b) or (c), in which R7 is hydrogen and R8 is R'8 and X is X'.

18. A compound according to any one of Claims 4 to 13, in which D is a radical of formula (d), R2 and R3 are R'2 and R3', D' is a radical of formula (a), in which n is 1 and m is 1 or n is 2 and m is 0, preferably the latter, R4 is hydrogen and R5 is -NHCOR6, Hal is chlorine and X is X'.

19. A compound according to any one of Claims 4 to 13, in which D is a radical of formula (e), in which R10 is P'10, R11 is block R11' and R,2 is R12', R2 and R3 are R2 and P'a, D' is a radical of formula (b) or (c), in which R7 is hydrogen and R8 is R'8, Hal is chlorine and X is X'.

20. A compound according to any one of Claims 4 to 13, in which D is a radical of formula (f), in which R14 is R',4 and R15 is R15', R16 is R16' and p is 1, R2 and R3 are R2 and R'3 and D' is a radical of formulae (b) or (c), in which R7 is hydrogen and R8 is R8', Hal is chlorine and X is X'.

21. A compound according to any one of Claims 4 to 13, in which D is a radical of formula (g) R2 and R3 are R'2 and R3', D' is a radical of formula (d) or (c) in which R8 is P'5, Hal is chlorine and X is X'.

22. A compound according to any one of Claims 14 to 21, in which X is a monohydroxysubstituted straight or branched chain C3-6alkylene.

23. - A compound according to any-one of Claims 14 to 22, in which R1, R2 and R3 are hydrogen.

24. The compound of formula

or a salt thereof.

25. The compound of formula

or a salt thereof.

26. The compound of formula

or a salt thereof.

27. A process for the production of a compound of formula I, comprising condensing a compound of formula II

in which F is D or D' with a compound of formula III

in which F, is D' when F is D or is D when F is D'.

28. A process for the production of a compound of formula I, as defined Claim 1, substantially as hereinbefore described with reference to any one of Examples 1 to 52.

29. A compound of formula I, as defined in Claim 1, whenever obtained by a process according to Claim 27 or 28.

30. A process for dyeing or printing nitrogen-containing or hydroxy-containing organic substrates comprising applying a compound according to any one of Claims 1 to 26 or 29 thereto, as dyeing or printing agent.

31. A process for dyeing or printing nitrogen-containing or hydroxy-containing organic substrates substantially as hereinbefore described with reference to the Application Example.

32. Dyed or printed substrates whenever obtained by a process according to Claim 30 or Claim 31.