GB2219804A

GB2219804A - Reactive dyes with cyanodihalopyrimidyl and chlorotriazinyl groups

Info

Publication number: GB2219804A
Application number: GB8913469A
Authority: GB
Inventors: Gunther Auerbach; Kurt Brenneisen; Markus Doerr; Paul Doswald; Markus Gisler; Werner Koch; Helmut Anton Moser; Roland Wald
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1988-06-14
Filing date: 1989-06-12
Publication date: 1989-12-20
Anticipated expiration: 2009-06-12
Also published as: FR2632651A1; PT90839A; HK134294A; IT1231922B; DE3918653A1; PT90839B; FR2632651B1; ES2016026A6; JPH0234667A; JP2641943B2; DE3918653C2; ZA894538B; GB2219804B; CH678186A5; CN1098121A; IT8948077A0; ATA144389A; EG19298A; GB8913469D0; AT398978B

Description

2 2 'I v 4 1 Case 150-5256 FIBRE-REACTIVE DYESTUFFS This invention relates

to chromophoric compounds containing fibre- reactive groups 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, this invention provides compounds of formula I Cl F X-N Alk N < \ CR 1 /RI N C 1 I a CN Cl -b in free acid or salt form, in which Fc is the radical of a water-soluble azo, formazan, phthalo- cyanine, azomethine, oxazine, thiazine, phenazine or tri- phenylmethane dye which is in metal-free or metal complex form, which radical may contain a further fibre-reactive group, each a, independently, is O or 1 and b is 1 or 2; each X, independently, is a direct bond, -CO or -SO 2-, each R 1, independently, is hydrogen, unsubstituted C 1 _ 4 alkyl or C 1 _ 4 alkyl which is monosubstituted by hydroxy, halogen, -503 H, -O 503 H or -COOH, and each Alk, independently, is C 2 _ 4 alkylene; 150-5256 each W, independently, is N Bl - I R 1 -N C 2-4 alkylene-N N-, I \ / R 1 N N- l \_or ( 503 H) N _- I R 1 -N N, k__ -N N C 2-_ 4 alkylene N -, I Rl -N N I (SO H) 3 m in which m is 0 or 1, and Bl is C 2 _ 6 alkylene, a C 2 _ 6 alkylene chain which is interrupted by -0 or -NR,-, C 3 _ 6 alkylene which is substituted by one or two hydroxy groups or by one carboxy group, -(CH 2)n R or (CH 2)n- R 2 n is 0, 1, 2, 3 or 4, and R 2 is hydrogen, C 1 _ 4 alkyl, Cl_ 4 alkoxy, -COOH or -503 H, and mixtures of compounds of formula I.

In the specification, any alkyl, alkenyl, alkynyl or alkylene group present is linear or branched unless indicated otherwise In any hydroxy-substituted alkyl or alkylene group which is attached to a nitrogen atom, the hydroxy group is preferably bound to a carbon atom which is not directly attached to the nitrogen atom In any alkylene group containing two hydroxy groups, the hydroxy groups are bound to different carbon atoms which are preferably not adjacent to each other In any alkylene chain interrupted by -0 or -NR 1 which is at- tached to a nitrogen atom, preferably the -0 or -NR 1 is bound to a carbon atom which is not directly attached to the nitrogen atom.

Any halogen is preferably fluorine, chlorine or bromine; more preferably, it is chlorine or bromine, and especially chlorine.

in which 2 - 3 150-5256 Fóis preferably the water-soluble radical of a metal-free or metal containing monoazo or disazo dye which when metallised is pref- erably in 1:1 copper complex or 1:2 chromium or 1:2 cobalt complex form, of a formazan, copper or nickel phthalocyanine or triphenedioxazine dye.

Each X, independently, is preferably a direct bond or -SO 2-.

Each Alk, independently, is preferably a C 2 _ 3 alkylene group.

Any alkyl as R 1 preferably contains 1 or 2 carbon atoms Any sub- stituted alkyl as R 1 is preferably C 1 _ 3 alkyl preferably containing one substituent selected from hydroxy, -SO 3 H, -O 503 H or -COOH, especially hydroxy.

Each R 1 is preferably Rla, where each Rl,, independently, is hydrogen, methyl, ethyl, 2-hydroxyethyl, -(CH 2)r-SO 3 H, -(CH 2)r-OSO 3 H or -(CH 2)q-COOH, in which r is 1 or 2 and q is 1, 2 or 3.

More preferably, each R 1 is Rib, where each Rlb, independently, is hydrogen, methyl, ethyl or 2-hydroxyethyl Most preferably each R 1 is hydrogen.

Each R 2 is preferably R 2 a, where each R 2 independently, is hydrogen, methyl, methoxy, -COOH or -SO 3 H More preferably each R 2 is R 2 b, where each R 2 b, independently, is hydrogen or -SO 3 H.

Each Bl is preferably Bla, where each B 1 i, independently, is -C 2 4 alkylene-, -C 2 -3 alkylene-O-C 2 _ 3 alkylene-, -C 2 3 alkylene-N-C 2 _ 3 alkylene-, monohydroxy-substituted -C 3 4 alkylene-, I Rlb -(CH 2)n or 2 nlin which nj is 0, 1, 2 or 3.

R 2 a R 2 a More preferably each Bl is Bib, where each Bib, independently, is -C 2-_ 3 alkylene-, monohydroxy-substituted -C 3-_ 4 alkylene-, 4 150-5256 (CH 2) - (CH 2) or N 2 in which N 2 is 0, I or 2.

R 2 b R 2 b Most preferably each Bl is BIó, where each B 1, independently, is -C 2-_ 3 alkylene or monohydroxy-substituted -C 3 _ 4 alkylene Each W is preferably V 1, where each W 1, independently, is -N-B 1,-N, -N N-, -N C 2 _ 3 alkylene -NN or I I \ I Rlb Rlb Rlb N N C 23 alkylene N Rib More preferably each W is W 2, where each W 2, independently, is -N -Bib N or -N N Most preferably each W is W 3, where Rib Rlb each W 3, independently, is -NH B 1 c NH-.

Preferred compounds of formula I in metal-free or metal complex form correspond to compounds of formulae ( 1) to ( 7) as defined below:Compounds ( 1) _ (Z)b DK N = N KK ( 1) in which DK is the radical of a benzenic or naphthalenic diazo component, KK is the radical of a benzenic, naphthalenic or heterocyclic coupling component or of a CH-acidic compound capable of being enolised, j I 150-5256 C 1 Z is N/ N CN C 1 in which W is as defined above, and b is 1 or 2, which one or two groups Z are bound to the diazo and/or coupling component by -N R 1 Preferably b is 1.

In a compound ( 1) DK is preferably one of the groups (a) to (h) in which each marked bond is attached to the azo group, R 3 l R 4 (a) ( 503 H)p R 50-Alkf-O (b) (SO 3 H)q (c) R R 2 R 4 (CH'2)n N- R 1 R 4 (CH)-N- R 1 -N )D ( CON"" R 9 (s 3 p)r id) ke) - = IF 150-5256 R I( 1 -N-(CH 2) (g) SO 3 H (h) R 51 in whic R R 3 R 4 R 13 Alk R 5 R 50 ch and R 2 are as defined above, is hydrogen, halogen, C 1 _ 4 alkyl, benzoylamino, -503 H or -COR 13, is hydrogen, halogen, C 1 _ 4 alkyl, is -OH, -0 Cl_ 4 alkyl or -NH 2, :l is -C 2-_ 3 alkylene, is hydrogen, -SO 3 H, C 1 _ 4 alkyl or is hydrogen or -SO 3 H, Cl_ 4 alkoxy, acetylamino, C 1 _ 4 alkoxy or -COR 13, C 2 _ 4 hydroxyalkyl, or R 51 is N ( 503 H) R 1 n is 0, 1, 2, 3 or 4, p is 0, 1 or 2, q is 1, 2 or 3, and r is 1 or 2; R I 1 -N_ (SO 3 H)r (f) NR 16 - R 1 150-5256 KK is preferably one of the groups (K 1) to (K 7) in which the marked carbon atom indicates the position where the coupling takes place, R < N (Kj) R R in which R, is as defined above, R 6 is hydrogen, C-l_ 4 alkyl or Cl_ 4 alkoxy, and R 7 is hydrogen, halogen, C_ 14 alkyl, Cl_ 4 alkoxy, -NHCO Cl_ 4 alkyl or -NHCONH 2; R 8 -CHCO-N / (K 2) R 1 I in which R 1 is as defined above, R 8 is hydrogen, halogen, Cl_ 4 alkyl or Cl_ 4 alkoxy, R 9 is hydrogen, halogen, C_ 14 alkyl, Cl-4 alkoxy, -C 00 OOH or -503 H, and R 10 o is hydrogen, -503 H or -NR 1 (Z); 0 H t N > O (K 3) N 0 H Rll / IN -Q 1 N 4 J 7 - 8 150-5256 in which R 1 I is -OH or -NH 2, R 12 is C 1 _ 4 alkyl or -COR 13, R R 8 R 13 is as defined above, 8 Q 1 is hydrogen, C 1 _ 4 alkyl or 9 R 14 R 8 and R 9 are as defined above, and R 14 is hydrogen, halogen, C 1 x 4 alkyl, -CONR 8 R 1 R R 9 -SO 3 H or -(B 3) -N (Z) in which R 1 and a are as R 1 defined above and B 3 is a divalent bridging group; Q 2 3 (Ks) HO I Q 4 in which Q 2 is hydrogen; C 1 _ 4 alkyl; C 5 _ 6 cycloalkyl; phenyl or phenyl(C 1 l_ 4 alkyl) in which each phenyl ring is un- substituted or substituted by 1-3 substituents selected from C 1 _ 4 alkyl, C 1 _ 4 alkoxy, halogen, -COOH and -503 H; -COR 13 or C 1 _ 4 alkyl monosubstituted by -503 H, -O 503 H or -COR 13, Q 3 is hydrogen, -CN, -503 H, -COR 13, C 1 _ 4 alkyl, C 14 alkyl monosubstituted by -OH, halogen, -CN, C 1 _ 4 alkoxy, R 9 20, -SO 3 H, -OSO 3 Hor-NH 2 ; -SO 2 NH 2, Ri lo O or 1 Ane, in which R 15 is hydrogen, C 1 _ 4 alkyl or C 2 _ 4 hydroxyalkyl, and 150-5256 Ane is a non-chromophoric anion, Q 4 is hydrogen, -B 2 N (Z), C 1 _ 6 alkyl, C 2 _ 4 alkenyl, R 1 C 2 _ 4 alkynyl, C 5-_ 6 cycloalkyl, phenyl or phenyl(Cl_ 4- alkyl) in which each phenyl ring is unsubstituted or substituted by 1-3 substituents selected from halogen, C 1 _ 4 alkyl, CI_ 4 alkoxy, -SO 3 H, -COOH and -N N(Z); or I NJ -C 1 _ 6 alkylene-Y in which Y is -COOH, -COO Cl_ 14 alkyl, -SO 3 H, -O 503 H, -OH, -CN, Cl_ 14 alkoxy, -NH 2 or a protonatable aliphatic, cyclo- aliphatic, aromatic or heterocyclic amino group or a quaternary ammonium group, and B 2 is C 2 _ 6 alkylene, monohydroxy-substituted C 3 _ 6 alkylene, a C 2 _ 6 alkylene chain which is interrupted by -0 or -NR 1-, I, -C 1-4 alkylene or (SO 3 H)m (SO 3 H) cl C 1-4 alkylene or (SO 3 H) -B 2 NR 1 (Z) is -C 2 _ 4 alkylene -NN (Z), and R 1, R 9, Ro 10 and R 13 are as defined above; NR OH NR c (K 6) SO 3 (SO 3 H) OH NHCOR 16 503 H< (K 7) S 3 (SO 3 H) 9 - 150-5256 in which R 16 is Cl_ 4 alkyl, phenyl or phenyl substituted by 1-3 substitu- ents selected from halogen, C 1-4 alkyl and Cl_ 4 alkoxy, and R 1, a and m are as defined above.

Compounds ( 2) R 6 R 6 x X N = N N=N ( 2)-Z ( 2) R 7 R 7 x ( 503 H)t in which R 6, R 7, R 1 and Z are as defined above, t is 2 or 3, and R 6 X, independently, has one of the significances of R 6 and R 7 x, independently, has one of the significances of R 7.

Preferred compounds ( 2) are those, in which each R 6, R 6 x and R 7 x is hydrogen.

As compounds ( 3) there are provided metal complexes, preferably 1:1 copper and 1:2 chromium or 1:2 cobalt complexes, based on the follow- ing metal-free compounds ( 3 a) or ( 3 b), OH NR_-Z A =N ( 3 a) 503 H (SO 3 H)m R 22 OH NH Ho 3 S N =N 3 ( 3 b) NR 1 Z - 11 150-5256 in which R 1, Z and m are as defined above, R 2 R 2 A is R or (S 3 H)m ( 503 H)q R 22 HO S, in which m and q are as defined above, R 17 ( 503 H)m R 17 is hydrogen, halogen, nitro, C 1 _ 4 alkyl, C 1 _ 4 alkoxy, -C O R 13, -SO 3 H or -NHCOCH 3, R 22 is OH, OCH 3 or NH 2, and R 13 is as defined above.

In a 1:2 chromium or 1:2 cobalt complex the two azo compounds are the same or different, i e, it is a symmetrical or asymmetrical 1:2 metal complex.

Particularly preferred are 1:1 copper complexes based on a com- pound ( 3 a) in which A is the radical of a benzenic diazo component and the radical of the naphthalenic coupling component is of the for- mula OH so 3 H N Ri Z Furthermore, 1:1 copper complexes corresponding to the following formulae ( 3 c) to ( 3 e): - cu O O R O N"=N - R ( 3 c) NR 1 Z SO 3 H (SO 3 H)r i 12 - in which R 50 is hydrogen or SO 3 H, and R 1, Z and r are as defined above; Cus R O N=N N N - NR Z R 52 ( 1 5 in which R 52 is hydrogen, m is O or 1, r m + r are 2 or 3, R 1, R 2, R 50 and Z D N=N in which D 3 is SO R 29 Cl-4 alkyl or Cl_ 4 alkoxy, is 1 or 2 and and are as defined above; 0 1/ 0 S 503 H N=N K NR Z 503 H 1 3 H or ( 503 H) R 29 is hydrogen, COOH or SO 3 H, R 30 is hydrogen, Cl_ 4 alkyl, Cl_ 4 alkoxy or -O-Alk 1-0 R 5, and t, R 5 and Alk 1 are as defined above, and R 1, R 52 and Z are as defined above.

Compounds ( 4) l(C ' H N OH 2 D 1-N=N NH N-D 2 SO H so 3 H 3 S 3 H 2) n-NR 1-Z lm l(CH 2) -N Ri-Zlm ( 4) 150-5256 ( 3 d) ( 3 e) wherein _ 150-5256 in which each D 1 and D 2, independently, is the radical of a diazo component of the aminobenzene or aminonaphthalene series, containing at least one sulpho, sulphonamido or carboxy group, each m is O or 1 with the proviso that at least one m is 1, and R 1, Z and N are as defined above.

D 1 is preferably Dla, where D 1 is a group of formula (ax) or (cx) R 18 ( 503 H) (So 3 H)m (ax) (cx) in which R 18 is sulpho, sulphonamido or -COR 13, R 19 is hydrogen, halogen, C 1 _ 4 alkyl, C 1 _ 4 alkoxy, -NHCOCH 3 or SO 3 H, R 13, m and p are as defined above, and m + p are 1 or 2.

D 2 is preferably D 2 a, where D 2 a is a group of formula (dx) R 2 R 18 / (dx) R 4 in which R 4 and R 18 are as defined above, the marked bond is attached to the azo group and the other free bond is attached to the reactive group.

More preferably, in the group (dx) R 18 is in the 2-position (with the azo group in the 1-position) and the free bond which is attached to the reactive group, is in the 4 or 5-position.

13 - 14 - 150-5256 Compounds ( 5) NR 1-Z ( 5) p in which one of X 1 and X 2 is -0 and the other is carboxy, each R 20 and R 21, independently, is hydrogen, halogen, C 1 _ 4 alkyl, C 1 _ 4 alkoxy, -COR 13 or -NHCO(Cl_ 4 alkyl), R 1, R 13, Z and m are as defined above, each p, independently, is 0, 1 or 2, and m + 2 p are at least 2.

Compounds ( 6) R 23 C 1 (SO 3 H)m ( 53)m C 1 R 23 (SO 3 H) M R 2 ( 6) X 3-Alk 2-NR 1-Z)2 in which Q is -0 or -S-, each R 23, independently, is hydrogen or -502 CH 2 CH 20503 H, each m, independently, is 0 or 1, each X 3, independently, is -502-, -NR 1, -CONR 1 or - 502 NR 1 in which the marked atom is attached to a carbon atom of the ring system, each Alk 2, independently, is C 2 _ 4 alkylene, and each R 1 and Z, independently, is as defined above, and mixtures of compounds ( 6).

I 150-5256 In a compound ( 6), preferably the two Z's are identical.

Compounds ( 7) ( 7) So 2 N Rl 2 1 (X 4 -a NR 1 Z R 26 hich c is 1, 2 or 3, and d is 0, 1 or 2, with the proviso that c + d do not exceed 3; Pc is the phthalocyanine radical, Me is copper, nickel, cobalt, iron or aluminium, R 24 and R 25, independently, is hydrogen or C 1 _ 6 alkyl, or -NR 24 R 25 is a saturated 5 or 6-membered heterocyclic ring which may contain one further -0 or -N in which R 31 is I R 31 hydrogen, C 1 _ 4 alkyl, 2-hydroxyethyl or 2-aminoethyl, R 26 is hydrogen, halogen, hydroxy, C 1 _ 4 alkyl, C 1 _ 4 alkoxy, -COOH or -SO 3 H, a is O or 1, X 4 is a divalent, optionally -N containing aliphatic, I R 1 araliphatic or heterocyclic bridging group, or is -N=N KK 2 in which KK 2 is R 12 or Q 2 lQ 3 a N HO O B 2- Rg, R 11, R 12, Q 2, -B 2-, -B 3 and a are as defined above, each marked carbon atom indicates the coupling position, in wl each - 150-5256 Q 3 a is hydrogen; -CN; -503 H; -COR 13; C 1 _ 4 alkyl; Cl_ 4 alkyl monosubstituted by hydroxy, halogen, -CN, Cl_ 4 alkoxy, R 9 -502 NH 2; Ror -SO 2 NH 2; 9 _C or -503 H, -O 503 H or -NH 2; Ane, in which R 9, R 13, Rls and Ane are as defined above, of compounds ( 7).

The fibre-reactive group Z is preferably Za corresponding to the formula C 1 -N N,i C CN C 1 Za À More preferably Z is Zb, where Zb is a group Za in which W 1 is W 2.

Most preferably it is Z=, where Zc, is a group Z in which W 1 is W 3.

Preferred compounds ( 1) are those corresponding to the formulae (la) to (ld): - Compounds of formula (la) DK 1 N = N KK 1 z a (la) in which Z is as defined above and is attached to DK 1 or KK 1, DK 1 is one of the groups (al) to (fl) and (hj) in which the marked bond is attached to the azo group: - and mixtures / \ 16 - R 15 _GNY k 17 - ( 503 H) 3 p Ra R 3 a (al) 150-5256 in which p is 0, 1 or 2, and each R 3 a and R 4,, independently, is hydrogen, chlorine, methyl, methoxy, ethoxy or -COOH; in which (SO 3 H) R 5 a O (CH 2) - (b l) m t R 5.

is O or 1, is 2 or 3, and is hydrogen, methyl, ethyl, -SO 3 H or 2-hydroxyethyl; in which m is O or 1, r is 1 or 2, and m + r are 2 or 3; in which Rib, R 4 a and p are as defined above; R I lb -N CONH,:

(SO 3 H)r R Ilb N) NHCO:

(SO 3 H)r (f 1) (ei) in which Rib and r are as defined above; SO 3 H -R 5 a C O t \-NHC Nl /a SN=C Cl.

in which R 51 i is ) N - ( 3 H)Rib ( 503 H)r (SO 3 H)r So 3 H / ( 503 H)r (c 1) (SO H) 4 a N- Rlb (dl) (h 1) 18 - 150-5256 R / 50 or and CH 3 SO 3 H Rs 50, Rib, a and r are as defined above; and KK 1 is one of the groups (K 2,), (K 4) and (K 5 s) as defined below or (K 3) as defined above: - R 8 a COCH R 1 3 / 9 a CHCONH R( 10 a (K 2) R N- I N R 12 a (K 4) Ra 8 a in which R 8 s is hydrogen, chlorine, methyl or methoxy, Rg 9 is hydrogen, chlorine, methyl, methoxy, -SO 3 H or -COOH, and R 10 oa is hydrogen, -503 H or -N-(Za); I Rlb in which R 11, Rs and R 9 are as defined above, R 12 a is methyl, -COOH or -CONH 2, and R 14 a is hydrogen, chlorine, methyl, ethyl, -SO 3 H or -N-(Z,); b Rlb in which Q 2, is hydrogen, methyl, ethyl, phenyl, -COR 13, -CH 2 SO 3 H or -CH 2 OSO 3 H, Q 3 b is hydrogen, -CN, -SO 3 H, -COR 13, methyl, ethyl, -CH 2503 H or -CH 2 NH 2, HO Q 4 a (Ks) Q 4 a is hydrogen, -B 2 a N(Za), methyl, ethyl, cyclohexyl, phenyl Rlb or phenyl(Cl_ 2 alkyl), in which latter two groups the phenyl ring is unsubstituted or substituted by 1 or 2 substituents selected from chlorine, methyl, methoxy, -503 H, -COOH, -NH 2 and -N-(Za), I Rlb or -C 1 l_ 4 alkylene-Y 2, B 2 a is -C 2 _ 4 alkylene-, monohydroxy-substituted -C 3 _ 4 alkylene-, 19 - 150-5256 -C 1 l-2 alkylene-or 2 alklene- (SO H) (SO 3 H) (S 3 H) or B 2 together with -N-(Za) to which it is attached, is I Rib -C 2 _ 3 alkylene -N N-(Za), Y 2 is -COOH, -SO 3 H, -OSO 3 H, -OH, -CN, methoxy or -NR 27 R 28, each R 27 and R 28, independently, is hydrogen; unsubstituted C 1 _ 4 alkyl; C 1 _ 4 alkyl monosubstituted by hydroxy, Cl_ 4 alkoxy, -COOH, -SO 3 H, -NH(C 1 l_ 4 alkyl) or N(C 1 _ 4 alkyl)2; unsubstituted cyclohexyl; cyclohexyl substituted by 1 to 3 methyl groups; phenyl or phenyl(C 1 _ 4 alkyl) in which each phenyl ring is unsubstituted or substituted by 1 or 2 substituents selected from halogen, preferably chlorine, Cl_ 4 alkyl, Cl_ 4 alkoxy, -SO 3 H and -COOH, or -NR 27 R 28 is a piperidine, morpholine or piperazine ring where each of these rings is unsubstituted or contains 1 to 3 methyl groups; compounds of formula (lb), R 6 N = N -Z R a (lb) Rlb 7 a ( 503 H)r( 503 H)m in which m + r are 2 or 3, R 6 i is hydrogen, methyl or methoxy and R 7 a is hydrogen, chlorine, methyl, methoxy, -NHCOCH 3 or 7 N -NHCONH 2; 4 u 150-5256 compounds of formula (lc), OH DK 2 NN GO N SO 3 H IN-Z 3 1 a Rib in which DK 2 is a group of formula (a 1), (bl) or (cl) as defined above; compounds of formula ( 1 d), OH NR c O O NR lb za / OH a DK 3 N=N a 3 ( 1 d) So 3 H SO 3 H in which the sulpho group is in the 3 or 4-position of the naphthyl ring, and DK 3 is a group of formula (a 2) or (c 2) SO 3 H in which R 3 and R 4 are as defined R above, 3 a R 4 a (a 2) (SO) SO 3 H) in which m + p are 1 or 2.

( 53 H) ( 53 H) m (c 2) 150-5256 Preferred compounds ( 2) correspond to formula ( 2 a), _ / = N< N = N < a ( 2 a) Ry Rlb R 7 a ( 503 H) (So 3 H)m in which R 7 is as defined above and m + r are 2 or 3.

Preferred compounds ( 3) are 1:1 copper complexes, based on the metal-free compounds ( 3 al) or ( 3 b 1), OH A 1-N N-( 3 a-) N SORH N-Z 503 H a Rlb in which R 22 a R 22 a R 22 a 2 A 1 is R 17 a or SO H H( 503 H)r ( 53 H)m 3 R 17 a is hydrogen, chlorine, bromine, nitro, methyl, methoxy, -503 H or -COOH, R 22 a is OH or OCH 3, and m + r are 2 or 3; R 22 a OH NH HOS NN 503 H 3 H ( 3 bj) s 3 H N Z I a Rlb in which R 22 a is as defined above.

21 - 22 - 150-5256 Furthermore, preferred compounds ( 3) are 1:1 copper complexes corresponding to the following formulae ( 3 cl), ( 3 dl) and ( 3 el), O,' O (SO H) R N-N _H H 503 H So 3 H N-Z 3 I a Rlb N-Z I a Rlb o/ O 503 H '/c 3 a =N -N N' - N-Z 52 a 503 H Il a 3 Rlb in which R 50 and R 52 a is R 2 a are as defined above, hydrogen, methyl or methoxy, and in which R 30 a is hydrogen, methyl or methoxy.

( 3 c 1) ( 3 d 1) ( 3 e 1) D 3 a is SO H 503 H 29 R a 150-5256 Preferred compounds ( 4) are those of formula ( 4 a), R H N OH D N = N N =N (a -N=N 2 ( 4 a) Z R Na 503 H 4 R SO H so 3 H 4 Rlb in which D 1,, R 4 and R 18 are as defined above; more preferred are compounds of formula ( 4 a) in which R 4 is hydrogen, and R 18 is in the 2-position and -N-Za is in the 4 or 5-position of I Rib the phenyl group.

Preferred compounds ( 5) are those in which each R 20 and R 21 is R 20, and R 21, where each R 20 o and R 21,, independently, is hydrogen, chlorine, methyl, methoxy, -COOH or -NHCOCH 3.

Preferred compounds ( 6) are those in which Q is -0-, each X 3, independently, is -N or -SO 2 N- I I Rib Rib each R 1, independently, is Rib, each Alk 2, independently, is -C 2 _ 3 alkylene-, and each Z, independently, is Za.

More preferred compounds ( 6) are those in which both groups con- taining Za are identical.

Preferred compounds ( 7) are those in which Me is copper or nickel, and each R 24 and R 25 is hydrogen.

23 - 24 150-5256 More preferred compounds ( 7) are those in which Me is copper or nickel, c is 2 or 3 and d is 0, each R 1, independently, is Rib, Z is Za, R 26 is hydrogen, -COOH or -SO 3 H and either a is 0, or a is 1 and X 4 is -N = N -KK 2 where KK 2 is Q 2 a i XQ 3 b HO T O B 2 a- in which Q 2 a, Q 3 b and -B 2 a are as defined above.

Furthermore, it is particularly preferred that in all above mentioned preferred metal-free compounds and metal complexes ( 1) Za is Zb; ( 2) Z is Zc; ( 3) Za is Zc and Rib is hydrogen.

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 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 t 150-5256 mixture of the above mentioned cations meaning that the compound of formula I can be in a mixed salt form.

The present invention further provides a process for the prepara- tion of compounds of formula I and mixtures thereof comprising re- acting a compound of formula II Fc Alk II in which Y 3 is -W-H or chlorine, and Fc, X, R 1, Alk, a, b and W are as defined above, or a mixture of compounds of formula II, if Y 3 is -W-H, with 5-cyano-2,4,6-trichloropyrimidine, or, if Y 3 is chlorine, with a compound of formula III III CN C 1 in which W is as defined above, using a 1:1 molar ratio for the compounds of formulae II and III.

Preferably, in a compound of formula II Y 3 is -W H The condensation reaction of a compound of formula II in which Y 3 is W H, with 5-cyano-2,4,6-trichloropyrimidine is suitably carried out at 0 to 40 C and at p H 7 to 9 Normally, water is used as reaction mediumf however, 5-cyano-2,4,6-trichloropyrimidine may also be used when dissolved in an organic solvent, for example in acetone.

- K 26 150-5256 Furthermore, disazo compounds of formula ( 4) may also be obtained by diazotizing a compound of formula IV H 2 N-D 2 -(CH 2 A)-NR 1-Z IV _m in which D 2, R 1, Z, m and N are as defined above, and alkaline cou- pling with a compound of formula V H 2 N OH D 1-N = N V SO 3 H l(CH 2) -NR -Zl so 3 H in which D 1, R 1, Z, m and N are as defined above.

The compounds of formula I may be isolated in accordance with known methods, for example, by conventional salting out with alkali lo metal salt, 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.

The starting compounds of formulae II, III, IV and V are either known or may be prepared in accordance with known methods using known starting material.

The compounds of formula I and mixtures thereof are useful as fibre-reactive dyestuffs for dyeing or printing hydroxy group or nitrogen containing organic substrates Preferred substrates are 27 - 150-5256 leather and fibre material containing or consisting of natural or synthetic polyamides and, particularly, of natural or regenerated cellulose such as cotton, viscose and spun rayon The most preferred substrate is textile material containing or consisting of 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 tempera- tures within the range of 30 to 801 C.

The compounds of this invention are well compatible with other fibre-reactive dyes; they may be applied per se or in combination with appropriate fibre-reactive dyestuffs of the same class having ana- logous dyeing properties, e g, concerning common fastness properties, extent of ability to exhaust from the dye bath onto the fibre etc The dyeings obtained with such combination mixtures have good fastness properties and are comparable to those obtained with a single dye- stuff.

In view of their notable build-up power the compounds of formula I give good exhaust and fixation yields The portion of unfixed dyestuff can be easily washed off the substrate The dyeings and prints obtain- ed show good dry and wet light fastness and also good wet fastness properties such as wash, water, sea water and sweat fastness They are resistant to oxidative influences, e g, chlorinated water, hypochlor- ite bleach and peroxide or perborate containing wash liquors.

150-5256 The following examples further serve to illustrate the invention.

In the examples all parts and percentages are by weight or volume The temperatures are in degrees Centigrade.

Example 1

To 18 3 parts ( 0 025 mole) of the compound of formula B SO 3 H C 1 N = N NH N (B) SO 3 H SO 3 H NHCONH 2 NHCH 2 CHNH 2 CH 3 in 500 parts of water a solution of 6 1 parts ( 20 % excess) of 5-cyano-2,4,6-trichloropyrimidine in acetone is added all at once at 250 The p H of the reaction mixture which decreases spontaneously is held at 7 to 7 5 by continuously adding a 20 % sodium carbonate solution Simul- taneously, the mixture is heated to reach a final temperature of 35 .

After 3 to 4 hours, the condensation reaction is terminated what is proved by thin layer chromatography.

For isolating the reaction product, the resulting orange-red dull solution is heated to 40 and stirred with filtering earth for about minutes It is then filtered clear, and sodium chloride (about 10 % by volume) is added to the filtrate whilst stirring The fine precipi- tate is filtered and dried at about 50 in vacuo The dyestuff of the formula So 3 H Cl- N N NH N SO 3 H 533 H NHCONH 2 NHCH 2 CHNH CH 3 CN C 1 thus obtained dyes cotton an orange shade The dyeings and prints on cotton obtained in accordance with conventional methods show good wet fastness properties and notably good light fastness, furthermore, they are resistant to oxidative influences.

28 - 29 - 150-5256 Preparation of the starting compound B a) 9 6 Parts of 2-amino-naphthalene-3,6,8-trisulphonic acid are dissolved in 60 parts of water at p H 12 by the addition of 4 3 parts of a 30 % sodium hydroxide solution To this solution, 11 parts of 30 % hydrochloric acid are added dropwise and a suspension is obtained which is well stirred Diazotisation is effected at 0-5 after the addition of 25 parts of ice by adding 6 5 parts of a 4 N sodium nitrite solution This diazonium salt solution is added to a suspension con- sisting of 3 9 parts of 3-aminophenylurea in 25 parts of ice water at 3-70 within 30 minutes During the addition, the p H is kept at 5 0 by adding 22 parts of a 20 % sodium carbonate solution A red solution is formed containing the aminoazo compound of formula A.

SO 3 H = N=N NH 2 2 (A) So 3 H So 3 H NHCONH 2 b) 5 1 Parts of cyanuric chloride are stirred into 30 parts of ice water during 30 minutes Subsequently, the dye solution obtained in step a) is added within 5 minutes, and condensation is effected at p H 6.0 in the presence of 8 parts of a 20 % sodium carbonate solution To the red-orange solution thus obtained, a solution is added containing 3.3 parts of 1,2-diaminopropane in 50 parts of ice water, the p H of which has been adjusted to 6 0 by adding 8 parts of 30 % hydrochloric acid Within one hour the temperature of the reaction mixture is slow- ly elevated to 48-50 Simultaneously, the p H of the mixture is kept at 6 0 by the addition of 20 parts of a 20 % sodium carbonate solution.

Before separating the orange dyestuff thus formed, its precipitation is completed by adding 100 parts of sodium chloride Thus, the com- pound of formula B is obtained.

Examples 2 to 200 By analogy with the method described in Example 1, using appro- priate starting compounds to form the desired chromophoric part F, further metal-free compounds of formula I may be prepared which are listed in the following Tables 1 to 11 At the top of each of these - 150-5256Tables the corresponding formula is given in which the symbols are as defined in the Table.

The compounds of Examples 2 to 200 may be applied to substrates containing or consisting of cellulose fibres, and particularly to textile material consisting of cotton, according to the conventional exhaust dyeing method or printing processes, where dyeings and prints of the indicated shade are obtained The dyeings and prints on cotton show good light and wet fastness properties and are resistant to oxidative influences.

The divalent group as defined in column W of Table 1 and also of every subsequent Tables may be an asymmetrical diamino group Nor- mally, the connection with a carbon atom of the triazine ring on the one side, and with a carbon atom of the pyrimidine ring on the other side, is effected in the given order However, depending on the prepa- ration of the starting compound, this connecting order may be revers- ed, i e pyrimidine / triazine ring, when the condensation product of the pyrimidine compound with the diamine is used as starting compound.

Table 1 / Compounds of formula (T 1) COCH 3 w-( DTI-N CHCON 1/\N-/N /% (i I 4 NH N(/ CN (T 1) C 1 Ex No DT 1 R 1 R 9 W (position) 2 H 03 S H -SO 3 H( 3) -NHCH 2 CHNH- CH 3 3 do H do -NHCH 2 CHCH 2 NH- OH Case 150-5256 Table 1 (continued) DT 1 ( RtRg (position) CH 3 COHN / so 3 H 503 H t 3 CH 3 -SO 3 H( 3) -NH(CH 2)3 N- I 3 CH 3 H H -NHCH 2 CH 2 NH- 503 H > COHN 53 so 3 H 53 H SO H so 3 H H -SO 3 H( 2) -NHCH 2 CHCH 2 NH- OH OH H H do.

do.

-NHCH 2 CHNH- IH 3 CH 3 SO H CH 33 3 - do.

SO H SO 3 H do.

do.

H -SO 3 H( 3) H H do.

H H SO 3 H( 3) H SO 3 H( 2) do.

-NH(CH 2)3 N- I CH 3 -NHCH 2 CHNH- I CH 3 -NHCH 2 CHCH 2 NH- I OH -NH(CH 2)3 N- IH 3 CH 3 Ex No.

31 - Case 150-5256 Table 1 (continued) Ex No DT 1 ( RsR 9 (position) SO 3 H S so O 3 H H H -NH(CH 2)3 N- CH 3 CH 3 H H H 503 H( 3) do.

do.

503 H SO H 3 SOIL do.

do.

H H CH 3 H H 503 H( 2) -NHCH 2 CH 2 NH- -NHCH 2 CHNH- I CH 3 do.

do.

The dyeings and prints on cotton obtained with the dyestuffs of Examples 2 to 19 have a greenish yellow shade.

W - 18 32 - 33 - Case 150-5256 Table 2 / Compounds of formula (T 2) C 1 C Isú W N CI Cl OH C 1 CN Ex No R 2 R 3 y R 2 COCH R 8 I 3 N = N CHCONH ' R 9 R 4 R 10 R 4 R 8 R 9 Rio H H CH 3 -SO 3 H do.

do.

H -NHCH 2 CH 2 NH- CH 3 -NHCH 2 CHNH- IH 3 C Hn 3 OCH 3 do.

do.

-NHCH 2 CHCH 2 NH- OH CH 3 OCH 3 H -SO 3 H H -SO 3 H -NH(CH 2)3 N- CH 3 The dyeings and prints on cotton obtained with the dyestuffs of Examples 20 to 25 are of a greenish yellow shade.

(T 2) H H H H 22 23 -SO 3 H do.

H H -SO 3 H CH 3 do.

H OCH 3 CH 3 H 34 - Case 150-5256 Table 3 / Compounds of formula (T 3) Cl Cl / 0 H NHN_ N O (T 3) C 1 CN / -NH so 3 H O 03 H Ex No W 26 -NHCH 2 CHCH 2 NH- OH 27 -NHCH 2 CHNH- CH 3 28 -NHCH 2 CH 2 NH- 29 -NH(CH 2)3 N- CH 3 With the dyestuffs of Examples 26 to 29 greenish yellow dyeings and prints on cotton are obtained.

- Case 150-5256 Table 4 / Compounds of formula (T 4) R OH R 3 C 1 D -N-N 5 N 12 NN= R 12 W N-Cl In the last column I the shade of each a is greenish yellow W.

CN Cl cotton dyeing (T 4) is given whereby and b Ex No.

is yellow.

position R 12 R 13 NH - H 035 33 do.

SO 3 H 3 H do.

do.

SO 3 H CH 3 do.

do.

H H H H H H -NHCH 2 CHNH- I CH 3 -NHCH 2 CHCH 2 NH- OH do.

4 -NHCH 2 CH 2 NH- -NHCH 2 CHNH- IH 3 CH 3 do.

3 H SO 3 H so 3 H 303 DT 4 I b b b b b b do.

H do.

b 36 - Case 150-5256 Table 4 (continued) position NH - SO H 37 CH 3 COHN '4 SO 3 H N Hco CH 3 39 HO 35 - NHCO- -COOH -SO 3 H do.

do.

-NHCH 2 CHCH 2 NH- OH OHI 4 -NHCH 2 CHNH- CH 3 CH 3 do.

do.

SO H 4 -NHCH 2 CH 2 NH b K Ex No.

DT 4 I a a a b R 12, R 13 I do do do.

Table 5 / Compounds of formula (T 5) C 1 N W C 1 CN N N =.

R 3 R 12 R 3 12 In the last column I the shade of each a is greenish yellow and b is yellow.

position Ex No W N=N R 2 cotton dyeing is given whereby I Lo Rll R 12 R 13 R 14 R 15 I -NHCH 2 CH 2 NH- do.

do.

-NHCH 2 CHCH 2 NH- OH 4 H 4 H H 503 H 4 H H H do OH do C 1 do.

6 5 3 Ri 5 (T 5) 42 43 44 46 5-SO 3 H do.

4-SO 3 H do.

5-SO 3 H 4-SO 3 H OH OH OH OH NH 2 do.

CH 3 do.

COOH CH 3 do.

do.

H Cl CH 3 C 1 H H b b 4-SO 3 H do.

do.

5-SO 3 H 3-SO 3 H 4-SO 3 H H 5-Cl H H H H a a b a C m 0 In tn Il LA n P CY% 48 do.

H a Table 5 (continued) position -N=N À R 2 Rll R 12 R 13 R 14 R 15 I 49 -NHCH 2 CHCH 2 NH- OH 4 H 5-SO 3 H OH CH 3 503 H 5-503 H do.

do.

-NHCH 2 CHNH- CH 3 4 H SO 3 H 4 H 53 do.

54 do.

do.

56 do.

57 do.

58 -NH(CH 2)3 N- CH 3 59 do.

-N NCH 2 CH 2 NH- \ / 61 -NH(CH 2)4 CHNH- COOH 4 H 4 H H SO 3 H H 4 H H 5-SO 3 H 4-SO 3 H do.

do.

5-SO 3 H H 4-SO 3 H 4 H 5-SO 3 H H 4-SO 3 H do.

OH OH OH OH OH do.

do.

COOH do.

CH 3 COOH SO 3 H Cl CH 3 H C 1 CH 3 5-SO 3 H do.

4-SO 3 H do.

do.

OH CH 3 Cl 5-SO 3 H OH do SO 3 H do.

OH do do do.

Ex No.

51 do.

4-SO 3 H 5-SO 3 H H OH OH NH 2 b COOH CH 3 do.

H SO 3 H H 4-SO 3 H do.

3-SO 3 H H H H b a b LAI 0 c I b b a a a b H H H H H H H H H a b I ul 0 to Ln U' 0 ' a , Case 150-5256 Table 6 / Compounds of formula (T 6) C 1 C 1 C N,\ C 1 >g N 3 W CO N C NH Nw K' C CN 3 ' CONHI R 14 (T 6) Rq N I N R 12 In the last a and b column I the shade of each cotton dyeing is given whereby is greenish yellow is yellow.

position position Ex No W -CONH- -NHCH 2 CH 2 NH- do.

do.

-N=N R 3 R 1, R 12 R 13 3 ' 3 4-SO 3 H 4 ' 4 3-SO 3 H 3 ' 4 do.

-NHCH 2 CHCH 2 NH- I OH 66 do.

67 do.

68 -NHCH 2 CHNH- I CH 3 69 do.

do.

3 ' 4 do.

4 ' 3 4-SO 3 H 4 ' 3 do.

3 ' 4 3-SO 3 H 3 ' 3 4-503 H 4 ' 4 3-SO 3 H 4 ' 4 do.

OH do -SO 3 H5-SO 3 H b OH OH OH NH 2 OH OH COOH do.

CH 3 do.

do.

COOH CH 3 H Cl Cl -SO 3 H CH 3 4-SO 3 H a do a do b 5-SO 3 H a 4-SO 3 H b do b 62 63 OH OH NH 2 R 14 I 4-SO 3 H a 5-SO 3 H b 4-SO 3 H a CH 3 do.

do.

-SO 3 H do.

H 39 - - Case 150-5256 Table 7 / Compounds of formula (T 7) C 1 Q 2 =Nt N = N-NHC \ R)O R WNI c 0 1 OH 3 4 I Q 4 CN C 1 R 4 Q 2 H CH 3 H do.

-SO 3 H do.

do do.

H do.

-SO 3 H do.

do -COOH H do.

H -CH 25 O 3 H H do.

Q 3 -SO 3 H do.

-CONH 2 do.

-CH 25 O 3 H H H H H -CONH 2 Q 4 CH 3 do.

do.

-CH 2 CH 3 do.

do.

H H CH 3 do.

W - -NHCH 2 CHCH 2 NH- OH -NHCH 2 CHNH- I CH 3 do.

do.

-NHCH 2 CH 2 NH- -NHCH 2 CHNH- I CH 3 do.

-NHCH 2 CHCH 2 NH- OH do.

-N NCH 2 CH 2 NH- do H CH 3 do -SO 3 Hdo.

do do do.

H H -CONH 2 -CH 2 CH 25 O 3 H -(CH 2)3 NHCH 3 -CH 2 CH 3 -N N- \/ -NH-e-NH- -NH(CH 2)4 CHNH- COOH COOH (T 7) Ex.

74 76 78 No R 3 -SO 3 H do.

do.

H -SO 3 H 41 - Case 150-5256 (continued) R 3 R 4 Q 2 Q 3 -SO 3 H -SO 3 H CH 3 do H do.

-CONH 2 -CH 2 CH 3 -CH 25 O 3 H H -HN j, NH- -HN NH- 503 H The dyeings and prints Examples 72 to 86 have on cotton obtained with each dyestuff of a greenish yellow shade.

Table 8 / Compounds of formula (T 8) C 1 N = N 7 K 17 NHCO 4 NH-< N OH SO 3 H R 4 N W Q 4 Ex No R 4 Q 3 Q 4 87 H 88 H 89 H H 91 H 92 -SO 3 H 93 do.

94 H CH 3 -CH 25 O 3 H do.

do.

-COOH CH 3 do.

do.

H -SO 3 H -CH 25 03 H do -CONH 2 do -CH 25 O 3 H H CH 3 -CH 2 CH 3 H H H -CH 2 CH 3 do.

4 3 3 3 4 -NHCH 2 CHCH 2 NH- OH do.

do.

-NHCH 2 CHNH- I CH 3 do.

do.

Table 7

Ex No.

Q 4 (T 8) position -NH- t_ 42 - Case 150-5256 Table 8 (continued) Ex No R 4 Q 2 Q 3 H -CH 2 SO 3 H-CONH 2 96 -503 H CH 3 H CH 3 -CH 2 CH 25 03 H -NHCH 2 CHNH- I CH 3 do.

97 H -CH 2 SO 3 H-CH 25 03 H 98 -503 H CH 3 -CONH 2 -CH 2 CH 25 03 H 4 -N NCH 2 CH 2 NH- \ / H -CH 2 CH 3 The dyeings Examples 87 and prints to 99 have on cotton obtained with each a greenish yellow shade.

dyestuff of Table 9 / Compounds of formula (T 9) D N=N WN Cl CN Cl In the last a and b column I the shade of each cotton dyeing is given whereby is greenish yellow is yellow.

Any marked carbon atom in a divalent group defined in column -B is bound to the nitrogen atom of the pyridone.

* position -NH- CH 3 99 H CH 3 N -N N- \__/ -Q 3 B (T 9) -NH-0-0- 43 - Case 150-5256 In Table 9 DT 9 may be a group C 1 RN 'k NH 51 R 50 SO 3 H depending on the definition of R 50 and R 51, the corresponding groups are signified by DD 1 to DD 12 In the following the significance of each group DD 1 to DD 12 is given.

SO 3 H DD 1 mit R 51 fur NH und R 50 fur H DD 2 mit R 51 fur DD 3 mit Rs 1 fur do.

SO 3 H N- CI C Hf 3 DD 4 mit Rs 51fur NH- SO 3 H 503 H SO 3 H DD 5 mit R 51 fur \ NH DD 6 mit R 51 fur H 03 S O -NH- 503 H SO 3 H DD 7 mit Rs 1 fur N 3 SO 3 H und R 50 fur 503 H und R 50 fur H und R 50 fur H und R 50 fur 503 H und R 50 fur H und R 50 fur H DD 8 mit R 51 fur do.

und R 50 far 503 H DD 9 mit Rsl fur DD 1 omit Rs 1 fur DDI 1 mit R 51 fur DD 12 mit R 51 fur Case 150-5256 HO S NH- 503 H So 3 H SO H NH- 503 H 503 H 503 H O NH- 503 H NH- 503 H 503 H und R 50 fur H und Ro 50 fur H und R 50 so f Ur 503 H und R 50 f Ur H Furthermore, Drg may be a group C 1 N N R 51 NH CONH R 50 503 H in the corresponding groups which are signified by DD 13 to DD 21, R 50 and R 51 are defined as follows: - R 51 S fur 503 H NH- DD 14 mit R 51 fur H 03 SO O NH- DD 15 mit R 51 fur SO H 503 H N- I 1 ki 13 und R 50 fur H und R 50 fur 503 H und R 50 fur H DD 13 mit 44 - Case 150-5256 DD 16 mit R 51 fur DD 17 mit Rs 51fur DD 18 mit Rs 1 fur DD 19 mit Rs 51fur SO H so 3 / \ NH- so 3 H 503 H t NH- 3 SO H o 3 NH- 503 H 503 H 503 H HNH- s 33 H und R 50 fur H und R 50 fur H und Rso f Ur H und R 50 fur SO 3 H DD 20 mit R 51 fur DD 21 mit und R 50 f Ur SO 3 H und R 50 fur H R 51 S fur 503 H - Case 150-5256 Table 9

Ex No.

DT 9 Q 2 Q 3 -B- CH 3 -CON 53 H 503 H HO 3 S do.

NH 2 -CH 2 CH 2 NH- H -CH 2 CHNH- CH 3 CH 3 do -CH 2 SO 3 H -_(CH 2)3 NCI 3 CH 3 -NHCH 2 CHCH 2 NH- OH -NHCH 2 CH 2 NH- -NHCH 2 CHNH- CI 3 CH 3 a a a SO 3 H SO 3 H SO 3 H 104 503 H SO 33 H SO 3 H SO 3 H do -SO 3 H -CH 2 CH 2-N N- do -CH 2 SO 3 H -CH 2 CH 2 NH- do -CONH 2 -'(CH 2)3 N- CI 3 C Hn 3 -NH(CH 2)3 N a I CH 3 -NHCH 2 CHCH 2 NH b OH -NHCH 2 CHNH a CH 3 SO H SH SOH 3 53 H -CH 25 O 3 H H -CH 2 CHNH- CI 3 CH 3 HO S 107 SO 3 H SO 3 H CH 3 H -CH 2 CH 2 NH- -NHCH 2 CH 2 NH- I 101 102 103 106 do.

b b k 46 - 47 - Case 150-5256 Table 9 (continued) Q 2 Q 3 -B- SO 3 H 108 S 3 H SO 3 H 109 H 03 S _C SOOH SO 3 H SO H /53 111 H / 3 - SO 3 H -CH 2 SO 3 H -CH 2 SO 3 H -CH 2 CH 2 NH N NCH 2 CH 2 NH- \__/ CH 3 -CONH 2 -CH 2 CHNH NH -NH- CI 3 CH 3 do.

b a a H -CH 2 CH 2 NHNHCH 2 CHNH- IH 3 CHM 3 CH 3 -CH 2 SO 3 H -(CH 2)3 NCH 3 b -NHCH 2 CHCH 2 NH- OH do.

HO 35 SO 3 H SO 3 H Cl / SO 3 H 114 HO 35 3 - NHCOCH 3 do -CH 2 CHNH NH(CH 2)3 N- IH 3 CH 3 CH 3 C H 13 -CH 2 SO 3 H -CONH 2 CH 3 -CH 2 SO 3 H -(CH 2)3 N do.

CH 3 do -NHCH 2 CH 2 NH- Ex No.

DT 9 I 112 113 b a a k Table 9 (continued) Ex No DT 9 HO 35 / NHCO O 503 H 116 H 035 NHCO - 117 DD 1 118 do.

119 do.

DD 2 121 do.

122 DD 3 123 DD 4 124 do.

DD 5 126 DD 6 127 do.

128 DD 7 129 DDM do.

48 - Q 2 Q 3 Case 150-5256 -B - I CH 3 -CH 2 SO 3 H -CH 2 CHNH NH(CH 2)3 N- I I CH 3 CH 3 do.

CH 3 do.

do.

a a a a a a a a do -(CH 2)3 N NHCH 2 CHNH- I I CH 3 CH 3 H -CH 2 CH 2 NH NHCH 2 CH 2 NH- -CONH 2 -_CH 2 CHNH do.

CH 3 H do -NHCH 2 CHNH- CH 3 -CONH 2 do -NH(CH 2)3 N- CH 3 -CH 2 SO 3 H -CH 2 CH 2 NHdo.

SO 3 H -CH 2 CHNH NHCH 2 CHCH 2 NH- I CH 3 OH H do -NHCH 2 CHNH- CH 3 -CONH 2 (CH 2)3 NH do.

-CH 2 SO 3 H -(CH 2)3)N do.

CH 3 -CONH 2 -CH 2 CH 2 NH do.

H do -NH(CH 2)3 N- I CH 3 H do -NHCH 2 CHNH- CH 3 -CONH 2 -CH 2 CHNH do.

I CH 3 H do -NHCH 2 CH 2 NH- a a a a a a a a Case 150-5256 (continued) DT 9 -CH 2 SO 3 H -CH 2 CH 2 NH- H do.

-CH 2 SO 3 H do.

-CONH 2 -(CH 2)3 N CH 3 do do.

H -'CH 2 CH 2 NH- -CH 2 SO 3 H do.

H do.

-CONH 2 -CH 2 CHNH- CH 3 H -CH 2 CH 2 NH- -CH 2 SO 3 H -(CH 2)3 N- CH 3 H do.

-CH 2 SO 3 H -CH 2 CH 2 NH- -CONH 2 do.

H -CH 2 CHNH- I CH 3 -CONH 2 do.

-NHCH 2 CHNH- I CH 3 do.

do.

-NH(CH 2)3 N- I CH 3 do.

do.

-NHCH 2 CHNH- CH 3 do.

do.

-NH(CH 2)3 N- I CH 3 -NHCH 2 CHNH- I CH 3 do.

do.

-NHCH 2 CH 2 NH- Table 9

Ex No.

Q 3 B - I a a a 131 132 133 134 136 137 138 139 141 142 143 144 146 DD 9 DD 10 DD 1 DD 12 DD 13 do.

DD 14 DD 15 DD 16 do.

DD 17 DD 1 a DD 19 DD 20 do.

DD 21 CH 3 do.

-CH 25 O 3 H do.

CH 3 do.

do.

a a a a a a a a a a a a a 49 - Case 150-5256 Table 10 / Compounds of formula (T 1 O) R 6 Cl SO 3 HN=N / NH -(/ N R 7 3 53 H ( 503 H)m NC In the last column I the shade b is yellow c is yellowish orange and d is orange.

of each cotton dyeing is given whereby Ex No position -N =N- 147 148 149 151 152 153 154 156 157 158 159 161 162 2 1 2 2 1 2 2 2 2 2 1 2 2 m R 6 (position) R 7 I d 1 ( 3) H -NHCONH 2 -NHCH 2 CHCH 2 NH- OH 1 ( 4) H 1 ( 3) o 1 ( 4) 1 ( 3) 1 ( 3) o 1 ( 3) 1 ( 4) 1 ( 3) 1 ( 3) 1 ( 3) 0 1 ( 4) 1 ( 3) H H H H H H CH 3 OCH 3 H H H H H H do.

do.

CH 3 do.

do.

H H CH 3 H -NHCOCH 3 do.

-NHCONH 2 do.

do.

H do.

do.

-NHCH 2 CHNH- I CH 3 do.

do.

d d b b b b b b b c c d d d b (T 10) - Case 150-5256 Table 10 (continued) Ex No position -N= N- m (position) 1 ( 3) H 1 ( 3) H 0 H 1 ( 3) H 1 ( 3) OCH 3 1 ( 3) H 1 ( 4) H 1 ( 3) H 1 ( 3) H 1 ( 3) H 1 ( 3) H 1 ( 4) H -NHCOCH 3 -NHCH 2 CHNH- CH 3 CH 3 -do.

do.

CH 3 H -NHCONH 2 do.

do.

CH 3 H do.

do.

-NHCH 2 CH 2 NH- do.

do.

-NHCONH 2 -N N- k_/ CH 3 do.

1 ( 3) H -NHCONH 2 -N NCH 2 CH 2 NH- 163 I 164 166 167 168 169 171 172 1 2 2 2 2 2 1 2 C C 173 C b b d d d b b 174 d b 51 - d 2 Case 150-5256 Table 11 / Compounds of formula (Tl) a N = N N =N e NH f 503 N _N= Ny ci (T 11) R (Tl O 37 ( 4 SO 3 H) d CN C 1 m Ex No (position) R 7 176 1 ( 4) CH 3 -NHCH 2 CHNH- OH 3 177 1 ( 4) -CH 2 CH 3 do.

178 0 CH 3 do.

179 1 ( 3) do do.

1 ( 4) do -NHCH 2 CHCH 2 NH- OH 181 1 ( 4) -CH 2 CH 3 do.

182 0 do do.

183 O CH 3 do.

184 1 ( 3) -CH 2 CH 3 do.

1 ( 4) CH 3 -NHCH 2 CH 2 NH- 186 1 ( 3) do do.

187 O do do.

188 1 ( 4) do -NH(CH 2)3 N- I CH 3 189 1 ( 4) do -N N- 1 ( 3) -CH 2 CH 3 do.

191 0 CH 3 -N NCH 2 CH 2 NH- \ / 192 1 ( 3) H -NH(CH 2)3 N- I CH 3 H do.

52 - 193 1 ( 4) 53 - Case 150-5256 Table 11 (continued) m Ex No (position) R 7 W - 194 1 ( 3) -NHCOCH 3 -NH(CH 2)3 NH- 1 ( 3) do -NHCH 2 CHNH- I CH 3 196 1 ( 3) -NHCONH 2 do.

197 1 ( 4) do do.

198 1 ( 3) H do.

199 1 ( 3) -NHCONH 2 -NH(CH 2)3 N- I CH 3 1 ( 3) do -NH(CH 2)3 NH- The dyeings and prints on cotton obtained with each dyestuff of Examples 176 to 200 have an orange shade.

Example 201

15.6 Parts ( 0 02 mole) of the dyestuff having the formula Cu SO H 0 O ' SOQE 3 /, 3 5030 / N NN / = N=N SO H CH 3 3 3 503 H are dissolved in 300 parts of water at p H 8 5-9 The p H is adjusted to 6.0 by adding a small amount hydrochloric acid To this solution 3 9 parts ( 0 02 mole plus 5 %) of cyanuric chloride are added, and the p H is held at 5 5-6 5 by the addition of sodium hydroxide solution whilst stirring at 10-15 After about one hour the reaction is completed.

To the resulting reaction mixture ( 0 02 mole) 1 6 parts ( 0 02 mole plus 10 %) of 1,2-diaminopropane are added Condensation is effected at 40-50 , and the p H is held at 5 5-6 5 by adding sodium hydroxide solution This reaction is completed after about two hours.

IC 54 150-5256 A fine dyestuff suspension is obtained to which ( 0 02 mole) 4 6 parts ( 0 02 mole plus 10 %) of 5-cyano-2,4,6-trichloropyrimidine are added This reaction is carried out at 15-200 and p H 8 5-9 0 By con- ventional salting out, filtering off and drying the dyestuff corre- sponding to the formula CU 53 H X " O SO H 3 3 N=N NNN N N N Cl so 3 H CH 3 N Ht r t 1 so 3 H N ON SOH 3 CH NHCH 2 C 111 H 7 CN C 1 is isolated which dyes cotton a blue shade These cotton dyeings have high light fastness and good wet fastness properties and are resistant to oxidative influences.

Examples 202 to 291 By analogy with the method described in Example 201, using appro- priate starting compounds to prepare the desired chromophoric part Fó, further metal-containing compounds of formula I may be prepared which are listed in the following Tables 12 to 17 At the top of each Table the corresponding formula is given in which the symbols are as defined in the Table.

The metal complexes of Examples 202-291 dye substrates containing or consisting of cellulose fibres, and particularly textile cotton fabrics, in the shade as indicated whereby the conventional exhaust dyeing method or printing processes are used The thus obtained dye- ings and prints on cotton have high light fastness and wet fastness properties and are resistant to oxidative influences.

Case 150-5256 Table 12 /

DT 12 N=N Ex No.

Compounds of formula (T 12) /,/ 503 ) N=N =N B 03 H C 1 NH -/ N N=I CN 1 CN Cl DT 12 SO 3 H so 3 H do.

do.

SO H HO 3 H O C S-0 CH 3 do.

do.

H H SO H 33 CH 3 O 3 - SO 3 H H 3 Cs O 3 H S 3 H/ 3 - 53 H do.

CH 3 do.

H -NHCH 2 CH 2 NH- -NH(CH 2)3 N- CH 3 -NHCH 2 CHCH 2 NH- OH -NHCH 2 CHNHI CH 3 do.

-NH(CH 2)3 N- I CH 3 do.

-NHCH 2 CHNH- I 3 CH 13 - (T 12) 202 203 204 205 206 207 208 209 Case 150-5256 (continued) DT 12 So H SO H d.

H CH 3 SO 3 H SO 3 3 SO H SO 3 H SO 3 H SSO 3 H 3 o 3 do.

do.

H -NHCH 2 CHNH- I CH 3 -NHCH 2 CH 2 NH- -NH(CH 2)3 N- I CH 3 -NHCH 2 CHCH 2 NH- I OH do.

Each dyestuff of Examples 202 to 214 dyes cotton a blue shade.

Table 13 / Compounds of formula (T 13) 346 (SO 3 H)q (T 13) CN I 56 Table 12

Ex No.

210 211 212 213 214 4 ( Case 150-5256 Table 13

Ex No R 2 R 29 215 216 H 2-OCH 3 217 218 219 220 221 222 223 224 225 H 2-OCH 3 2-CH 3 H H H H 2-OCH 3 do.

226 do.

H 3-SO 3 H do.

H H 2-SO 3 H do.

do.

3-SO 3 H do.

do.

R 52 H CH 3 H CH 3 H H H CH 3 H H H H position -NH- q (position) 4 -NHCH 2 CH 2 NH- -NHCH 2 CHNH- I CH 3 do.

4 -NH(CH 2)3 N- CH 3 do.

4 -NH(CH 2)3 NH- 4 -NHCH 2 CHNH- I CH 3 do.

4 do.

do.

-NH(CH 2)3 N- I C H 3 -NHCH 2 CH 2 NH- 2 ( 3,6) 2 ( 3,8) 3 ( 3,6,8) do.

2 ( 4,6) 2 ( 3,8) do.

2 ( 3,6) 3 ( 3,6,8) do.

do.

The dyestuffs of Examples 215 to 226 dye cotton a blue shade.

Table 14 / Compounds of formula (T 14) Cu -1 NN -' -N NX 3 R N C 1 N / N (T 14) 57 - Case 150-5256 58 - Table 14 position Ex No SO 3 H U - H -NHCH 2 CHNH- I CH 3 CH 3 do.

H do.

CH 3 do.

H do.

CH 3 do.

H -NHCH 2 CHCH 2 NH- OH do.

do.

-NHCH 2 CH 2 NH- do.

do.

-NH(CH 2)3 NH- do.

do.

-NH(CH 2)3 N- CH 3 H -N N- The dyestuffs of Examples 227 to 250 dye cotton a ruby-red shade.

R 17 227 H 228 229 230 231 232 233 234 235 236 4 6 4 4 6 4 4 4 H H 6-Cl do.

4-Cl 6-COOH 6-SO 3 H do.

H 237 238 239 240 241 242 243 244 245 246 247 248 249 6 6 4 4 4 4 4 4 6 4 4 4 H H H H H H H H H H H H H H 4-CH 3 6-Cl 6-SO 3 H do.

H 6-NO 2 6-Cl 4-Cl H 6-Cl 6-SO 3 H do.

do.

250 Case 150-5256 Table 15 / Compounds of formula (T 15) (T 15) Ex No.

-NHCH 2 CH 2 NH- -NHCH 2 CHCH 2 NH- OH -NH(CH 2)3 NH- -NHCH 2 CHNH- I CH 3 -NH(CH 2)3 N- CH 3 /-N - -N N- \/ The dyestuffs of Examples 251 to 256 dye cotton a dark blue shade.

Table 16 / Compounds of formula (T 16) (T 16) N C 1 CN C 1 59 - HO 35 o 503 H 251 252 253 254 255 256 Case 150-5256 In the last column I the shade of each cotton dyeing is given whereby g is ruby and h is violet.

Table 16 position Ex No R 50 -NH U r (position) I 257 5-SO 3 H 3 -NHCH 2 CH 2 NH 1 ( 6) g 258 do 3 -NHCH 2 CHNH do g I CH 3 259 3-SO 3 H 5 do do g 260 do 5 -NHCH 2 CHCH 2 NH do g OH 261 5-SO 3 H 3 do do g 262 do 3 -NH(CH 2)3 N do g I CH 3 263 H 4 do 2 ( 6,8) h 264 H 4 -NHCH 2 CHNH do h CH 3 265 H 5 do do h 266 H 4 -NHCH 2 CH 2 NH do h 267 H 4 -NH(CH 2)3 NH do h 268 H 4 -NH(CH 2)3 N do h CH 3 Table 17 / Compounds of formula (T 17) C C 4 N l CN C 1 (T 17) Table 17 p Ex No (position) X 1 position m X 2 -NH (position) 2 ( 3 ',5 ')-0 COOH 4 do do do 4 do do.

do do.

1 ( 4 ') do.

do.

-COOH- do.

do.

do do.

do.

1 ( 5 ') do.

do.

0 do 4 do 4 do 4 -O- do.

do.

0 3 3 do 3 do.

do.

2-SO 3 H do.

do.

3-SO 3 H do.

1 ( 5) H do H do H do.

do.

3 3 3 H 3-SO 3 H 2-Cl 2-Cl 2-SO 3 H H -NHCH 2 CH 2 NH- H -NHCH 2 CHCH 2 NH- I OH H -NHCH 2 CHNH- I CH 3 H do.

H -NH(CH 2)3 N- I CH 3 H -NHCH 2 CH 2 NH- H -NH(CH 2)3 NH- H -NHCH 2 CHCH 2 NH- OH H -NHCH 2 CHNH- CH 3 CH 3 H H 5-C 1 H do.

do.

269 270 R 20 R 21 271 U - 272 273 274 275 276 277 278 279 280 281 I 0 Cn In esn 0 s Ln a% Table 17 (continued) p Ex No (position) X 1 position X 2 -NH- m (position) -COOH -O- do do.

do do ' do do.

do do.

-O COOH- do do.

do do.

3 3 3 1 ( 5) 3-SO 3 H do 4-SO 3 H do 4-CH 3 do 4-OCH 3 do 3-CH 3 1 ( 5) 2-CH 3 1 ( 3) H do 2-CH 3 do 4-SO 3 H 1 ( 5) H H -NHCH 2 CHCH 2 NH- OH H do.

H -NHCH 2 CH 2 NH- H do.

4-Cl -NH(CH 2)3 N- I CH 3 H -NHCH 2 CHNH- CH 3 H do.

H -NHCH 2 CHCH 2 NH- OH H -NHCH 2 CH 2 NH- H do.

., R 20 282 283 284 285 286 287 288 289 290 291 1 ( 5 ') do.

do.

1 ( 4 ') i ( 5 ') do.

do.

*I a I l'.

0 m I-A Lni 0 Ln U' G' 63 - 150-5256 The dyestuffs of Examples 269 to 291 dye cotton a blue shade.

Example 292

45.3 Parts of the monoazo dyestuff of the formula 3 OH CH 30 N =N 3 I H 508 N 2 prepared in accordance with known methods, are dissolved in 700 parts of water Within 30 minutes 18 5 parts of solid cyanuric chloride are added at 20-25 The mixture is stirred at p H 6 0-6 5 until a free amino group is no longer detectable Subsequently, 11 1 parts of 1,2diaminopropane are added, and the reaction mixture is stirred for two hours whereby a p H of 7 0 is held by the addition of dilute sodium carbonate solution The condensation product is salted out by adding sodium chloride and filtered off The wet paste thus obtained is dis- solved in 900 parts of water To this solution 24 9 parts of 5-cyano2,4,6-trichloropyrimidine are added and stirring is effected for two hours at 0-5 During the course of reaction the p H is kept at 8-9 by adding dilute sodium carbonate solution The resultant dyestuff is precipitated with sodium chloride and isolated It corresponds to the formula 503 H OH CH O /' NN C 1 3 IN So 3 H NH d NHCH CHNH C 1 2, CH 3 CN C 1 The dyestuff when dried is a dark red powder which dissolves in water showing a red colour and dyes cotton a scarlet shade These dyeings have good light and wet fastness properties and are resistant to oxi- dative influences.

64 Case 150-5256 Examples 293 to 319 By analogy with the method described in Example 292, using appro- priate starting compounds, further compounds of formula I may be pre- pared They correspond to formula (T 18) 503 H OH R N =N Cl 534 H / (T 18) CN C 1 in which the symbols are as defined in Table 18 below The cotton dyeings obtained with the dyestuffs of Examples 293 to 319 have good light and wet fastness properties and are resistant to oxidative in- fluences.

In the last column I the shade of each cotton dyeing is given whereby d is orange and k is scarlet.

Table 18 / Compounds of formula (T 18) Ex No R 3 R 4 W I 293 OC 2 H 5 H -NHCH 2 CHNH k I CR 3 294 OCH 3 SO 3 H do k 295 -OC 2 H 4 OH H do k 296 OCH 3 H -NHCR 2 CHCH 2 NH k OH 297 do 503 H do k 298 -OC 2 H 4 OH H do k 299 OCH 3 H -NHCH 2 CH 2 NH k % - Case 150-5256 (continued) R 3 OCH 3 OC 2 H 5 -OC 2 H 4 OH OCH 3 do.

-OC 2 H 4 OH 0 C 2 H 5 OCH 3 do.

-0 C 2 H 4 OH -OC 2 H 4 O C 2 H 4 OH do.

do.

CH 3 do do do do.

SO 3 H H H H SO 3 H H H H 503 H H H H H H H 503 H do.

do.

lo.

H -NHCH 2 CH 2 NH- do.

do.

-NH(CH 2)3 NH- do.

do.

-NH(CH 2)3 N- I CH 3 -N N- \J/ do.

do.

-NHCH 2 CH 2 NH- -NH(CH 2)3 NH- -NHCH 2 CHCH 2 NH- OH -NHCH 2 CHNH- I CH 3 do.

-NHCH 2 CHCH 2 NH- OH -NHCH 2 CH 2 NH- -NH(CH 2)3 N- CH 3 do.

Example 320

Parts of cyanuric chloride are stirred to a homogeneous suspens- ion in a mixture of 10 parts of water and 20 parts of ice To this suspension a neutral solution (of p H 7) of 30 parts of the tetrasodium salt of the dyestuff having the formula Table 18

Ex No.

I 300 301 302 303 304 305 306 307 308 309 310 311 312 313 314 315 316 317 318 319 k k k k k k k k k k k k k k k d d d d d 66 - 150-5256 SO 3 H OH NH a N, =Ne 3 in 160 parts of water are added and stirring is effected at 5 O and p H 5.5-6 0 until the free amino group is no longer detectable At p H 6.5-7 0 the temperature is slowly elevated to 15 and then 3 25 parts of 1,2-diaminopropane are added The p H is kept at 6 0 by adding hydrochloric acid The mixture is heated at 50 for three hours, after this time the reaction is completed Then, 70 parts of sodium chloride are added, and the red suspension is filtered The filter cake is washed with 500 parts of a 20 % sodium chloride solution The resultant paste is brought into 500 parts of water and 4 5 parts of 5-cyano2,4,6-trichloropyrimidine are added Stirring is effected for 12 hours at 20 , until the reaction is complete and then 80 parts of sodium chloride are added The dyestuff thus obtained is precipitated and filtered; it corresponds to the formula 503 N< SO H 3 = -N C 1 The dyestuff when dried is a dark red powder which dissolves in water showing a red colour and dyes cotton a bluish-red shade These cotton dyeings have notably good general fastness properties.

Examples 321 to 416 By analogy with the method described in Example 320, using appro- priate starting compounds, further compounds of formula I may be pre- pared which are listed in Tables 19 to 22 below At the top of each Table the corresponding formula is given in which the symbols are as defined in the following Table The dyestuffs of Examples 321 to 416 dye cellulose fibres and particularly cotton using the conventional exhaust dyeing methedre Aci ihese dyeings are bluish-red and have good fastness properties.

t 67 - Table 19 / Compounds of formula (T 19) SO 3 H Case 150-5256 m position of the SO 3 H group(s) -NHCH 2 CHNH- I CH 3 -NHCH 2 CHCH 2 NH- OH do.

do.

-N N- \ J do.

-NHCH 2 CH 2 NH- do.

do.

-NH(CH 2)3 NH- do.

-NH(CH 2)3 N- CH 3 do.

do.

-NHCH 2 CH 2 N- I CH 2 CH 2 OH -NHCH 2 CHNH- IH 3 C Hn 3 (SO 3 H)m C 1 Ex No.

(T 19) CN C 1 321 322 323 324 325 326 327 328 329 330 331 332 333 334 335 336 337 1 0 1 1 0 1 1 1 1 1,5 3,6 1,5 1 1,5 4,8 1 1,5 1,5 3,6 4,8 4,8 68 Case 150-5256 Table 20 / Compounds of formula (T 20) C 1 (SO H),N 23 m HO INH 4 N 4 N=-N N i(T 20) 3 W m R 34 03 53 H R 4 CN C 1 Ex, No m (position R 3 R 4 U - 503 H) 338 1 ( 2) H H -N N- 339 do 5-SO 3 H H do.

340 do do 4-CH 3 do.

341 do do 4-OCH 3 do.

342 do H 4-CH 3 do.

343 do H 4-OCH 3 do.

344 do 4-SO 3 H H do.

345 do H H -NHCH 2 CH 2 N- CH 2 CH 2 OH 346 do H 4-OCH 3 do.

347 do 5-SO 3 H H do.

348 do H 4-CH 3 -NH(CH 2)3 N- I CH 3 349 do H 4-OCH 3 do.

350 do H H do.

351 do 5-503 H H do.

352 do 4-SO 3 H H do.

353 0 2-COOH H do.

354 0 3-COOH H do.355 0 4-COOH H do.

356 1 ( 2) 5-SO 3 H 4-OCH 3 -NHCH 2 CHCH 2 NH- OH 357 do H H do.

358 do H 4-CH 3 do.

Case 150-5256 Table 20 (continued) Ex No m (position R 3 R 4 U - 503 H) 359 1 ( 2) H 4-OCH 3 -NHCH 2 CHCH 2 NH- OH 360 do 4-SO 3 H H do.

361 0 3-COOH H do.

362 1 ( 2) H H -NHCH 2 CHNH- I CH 3 363 do 5-SO 3 H H do.

364 do do 4-CH 3 do.

365 do 4-SO 3 H H do.

366 O 2-COOH H do.

367 0 3-C 00 OOHH do.

368 0 4-COOH H do.

369 1 ( 2) H H -NHCH 2 CH 2 NH- 370 do H 4-OCH 3 do.

371 0 2-COOH H do.

372 1 ( 2) 5-SO 3 H H -NH(CH 2)3 NH- Table 21 / Compounds of formula (T 21) C 1 N; N X 3 OH NHCOR 16 (T 21) IN N Cl -< W NH Z N = N SOH 503 H C 1CN 33 Ex No -W R 16 373 -NHCH 2 CH 2 NH methyl 374 do ethyl 375 do phenyl 69 - Case 150-5256 - Table 21 (continued) Ex No W R 16 376 -NHCH 2 CHNH phenyl I CH 3 377 do methyl 378 do ethyl 379 -NH(CH 2)3 N methyl CH 3 380 do phenyl 381 -NHCH 2 CHCH 2 NH do.

OH 382 do ethyl 383 -N N methyl \/ 384 -NH(CH 2)3 NH phenyl Table 22 / Compounds of formula (T 22) 0 HO NHC N 4, ST ", N 3 NH 41 N (T 22) 503 H 71 - Case 150-5256 position position 503 H -NH- DT 22 SO H 3 -NHCH 2 CH 2 NH- 503 H do.

do.

503 H 503 H do.

do.

SO H SO H 3 do.

do.

3 4 4 do.

3 -NH(CH 2)3 N- I CH 3 3 -N-N N- \ /j 3 -NHCH 2 CHCH 2 NH- OH 3 -NHCH 2 CHNH- I CH 3 3 do.

4 do.

3 3 4 3 4 do.

do.

-NH(CH 2)3 N- CH 3 CH 3 Table 22

Ex No.

385 386 387 388 389 390 391 392 393 394 395 396 397 398 Case 150-5256 2 (continued) DT 22 SO 3 H 53 H so 3 H do.

do.

SO H /3 CH 30 do.

do.

SO 3 H H 3 C So 3 H do.

SO 3 H HO 35 do.

do.

HOOC / - position position SO 3 H -NH- 3 4 -NH(CH 2)3 N- I CH 3 3 -NHCH 2 CH 2 NH- 3 -NHCH 2 CHNH- I CH 3 4 -NHCH 2 CHCH 2 NH- OH 3 -NHCH 2 CHCH 2 NH- OH 4 -NHCH 2 CHNH- I CH 3 4 do.

do.

3 -NHCH 2 CH 2 NH- do.

do.

-NHCH 2 CHNH- I CH 3 -NH(CH 2)3 N- I CH 3 do.

72 - Table 2

Ex No.

399 400 401 402 403 404 405 406 407 408 409 410 411 412 Case 150-5256 Table 22 (continued) position position Ex No DT 22 SO 3 H -NH W- COOH 413 Gb 3 4 -NHCH 2 CHNH- CH 3 SO 3 H 3 414 3 3 do.

415 do 4 4 -NH(CH 2)3 NH- 416 do 3 4 -NHCH 2 CHCH 2 NH- OH Example 417

212 Parts of cyanuric chloride are stirred in a mixture of 560 parts of ice and 200 parts of water for 45 minutes A solution con- sisting of 190 parts of 2,4-diaminobenzene-1-sulphonic acid in 920 parts of water and 112 parts of a 30 % sodium hydroxide solution is added and this mixture is stirred for 6 hours while cooling with an ice-bath Subsequently, the white suspension is indirectly diazotized.

In the meantime, 140 parts of 4-aminobenzoic acid are diazotized in accordance with known methods and are coupled,with 320 parts of 1amino-8-hydroxynaphthalene-3,6-disulphonic acid under acid reaction conditions To the red suspension obtained the above diazo solution is added, and alkaline coupling is effected.

A blue solution is obtained to which 120 parts of 1,2-diamino- propane are added Condensation is effected during two hours The reaction mixture is then salted out with sodium chloride ( 25 % by volume) and filtered The blue filter cake is redissolved in water using the ten-fold amount.

To this aqueous solution a suspension of 175 parts of 5-cyano2,4,6-trichloropyrimidine in 350 parts of water and 150 parts of ice which has been stirred for 45 minutes, is added within two hours The p H of the reaction mixture is then held at 9 for three hours The 73 - 150-5256 product thus obtained is salted out by adding sodium chloride ( 10 % by volume) and filtered and the filter cake is dried at 40 in vacuo The dyestuff having the formula Cl HOOC e N= N N NH / N SO 3-'H SO 3 NHCH 2 CHNH N, SO 3 H so 3 H 3 2 CE 3 = CN C 1 dyes cellulose fibres and particularly cotton a navy shade These dyeings have good fastness properties such as light and wet fastness properties and are resistant to oxidative influences.

Examples 418 to 456 By analogy with the method described in Example 417, using appro- priate starting compounds, further compounds of formula I may be pre- pared They correspond to formula (T 23) R 3 2 HN OH __ 32 2 /\C N = <N N = 4 C 1 R; 5 NH d N (T 23) 3 R 4 SO 3 H SO 3 H N C 1 CN C 1 in which the symbols are as defined in Table 23 below The dyestuffs of Examples 418 to 456 dye cellulose fibres and particularly cotton a navy shade using the conventional exhaust dyeing method These dyeings have notably good general fastness properties.

74 - Case 150-5256 Table 23 / Compounds of formula (T 23) Ex No R 3 R 4 position -NH- 503 H 4 do.

4 COOH 4 503 H do.

4 do.

do.

4 COOH SO 3 H 4 COOH 4 do.

4 SO 3 H 4 do.

do.

4 do.

4 COOH SO 3 H do.

do.

-NH p NH- SO 3 H do.

do.

-NHCH 2 CHNH- I CH 3 do.

do.

-NHCH 2 CHCH 2 NH- OH do.

do.

-NHCH 2 CH 2 NH- do.

do.

-NH(CH 2)3 NH- 418 419 420 421 422 423 424 425 426 427 428 429 430 431 432 433 434 435 436 437 438 439 440 441 442 443 444 4-SO 3 H 3-COOH 4-COOH do.

3-SO 3 H 5-COOH do.

do.

3-COOH 4-SO 3 H 2-SO 3 H 4-SO 3 H 2-SO 3 H 4-SO 3 H 2-SO 3 H 5-COOH 4-COOH 4-SO 3 H 3-COOH 3-COOH 3-SO 3 H do.

do.

5-COOH 5-SO 3 H 3-COOH 2-SO 3 H H H H H H 2-Cl do.

do.

H H 4-Cl H 4-Cl H 4-Cl 2-Cl H H H H H H H 2-Cl do.

H 4-Cl - Case 150-5256 Table 23 (continued) Ex No R 3 R 4 position -NH- 4 503 H 4 COOH SO 3 H do.

do.

COOH 4 do.

503 H 4 COOH SO 3 H 4 COOH do.

-NH(CH 2)3 NH- -NH(CH 2)3 N- I CH 3 do.

do.

-N N- do.\ do.

do.

-NH(CH 2)4 CHNH- I COOH do.

do.

Example 457

65.9 Parts of the dyestuff of the formula HO S H 2 N(CH 2)H 035 HN H 2 N (CH 2) 3 HN C 1 NH(CH 2) 3 NH 2 prepared in accordance with known methods are dissolved in 1200 parts of water At 20-250 37 parts of solid cyanuric chloride are added within 30 minutes The mixture is stirred for one hour at p H 6 0-6 5 which is held by continuously adding a dilute sodium carbonate solu- tion 22 2 Parts of 1,2-diaminopropane are added, and stirring is effected at 40-50 o for two hours while holding the p H at 7 0 by the addition of a dilute sodium carbonate solution The condensation product is salted out with sodium chloride and filtered The resultant R 5 W - 2-C 1 H 445 446 447 448 449 450 451 452 453 454 455 456 5-SO 3 H 4-COOH 5-SO 3 H 4-COOH 5-COOH 3-COOH 3-SO 3 H do.

5-COOH 4-COOH 5-SO 3 H 2-SO 3 H 2-C 1 H 2-Cl H H H 2-C 1 H 2-Cl 4-Cl 76 Case 150-5256 paste is redissolved in 1400 parts of water To this solution 49 5 parts of 5-cyano-2,4,6-trichloropyrimidine are added, and stirring is effected for two hours at 5-10 During the course of the reaction the p H is kept at 8-9 by the addition of a dilute sodium carbonate solu- tion The resultant dyestuff is precipitated by adding sodium chloride and isolated It corresponds to the formula Cl SO H C 1 3 N 0 N C 1 C 1 SOH R 3 NH(CH 2)3 NH-</ N N=f C 1 NHCH 2 CHN-H CH 3 CN C 1 -2 and when dried it is a black powder which dissolves in water with deep-blue colour The dyestuff dyes cotton a deep-blue shade These dyeings have very good light and wet fastness properties.

Examples 458 to 472 By a method analogous to that described in Example 457 further compounds of formula I may be prepared They correspond to formula (T 24) R Cl (SO 3 H)m N O A O N t C 1 ( 53 H)m C 1 R 1-NH(CH 2)3 NH N _ _ NC 1 (T 24) Ws N CN C 1 -2 in which the symbols are as defined in Table 24 below The dyestuffs 77 - I 78 - Case 150-5256 of Examples 458 to 472 dye cotton a deep-blue shade These dyeings have good light and wet fastness properties.

/ Compounds of formula (T 24) m R 1 W - H H H H H -SO 2 CH 2 CH 205 03 H do.

do.

-NHCH 2 CH 2 NH- -NH(CH 2)3 NH- -NH(CH 2)3 N- CH 3 -NHCH 2 CHCH 2 NH- OH -N N- do.

-NHCH 2 CH 2 NH- -NH(CH 2)3 NH- -NHCH 2 CHCH 2 NH- OH -NHCH 2 CHNH- CH 3 do.

-NHCH 2 CHCH 2 NH- OH -NHCH 2 CH 2 NH- -NH(CH 2)3 NH- -N N- Example 473

25.7 Parts ( 0 025 mole) of the dye base, prepared in accordance with known methods by sulphochlorinating of copper phthalocyanine and then reacting with 1,3-diaminobenzene-4-sulphonic acid, containing per molecule an average value of about 2 5 sulphonic acid groups and 1 sulphonamido group, are dissolved in 200 parts of water at p H 6 5-7 0.

After the addition of 150 parts of ice, at 0-5 4 6 parts of cyanuric chloride are added and stirring is effected for two hours at p H 6 0Table 24

Ex No.

458 459 460 461 462 463 464 465 466 467 468 469 470 471 472 1 1 1 0 0 0 1 1 ( 79 150-5256 6.5 2 8 Parts of 1,2-diaminopropane are then added and, after having stirred for one hour at 0-5 , the temperature is raised to 30-350 within two hours and the p H is adjusted to 7 5-8 0 by adding a 20 % sodium carbonate solution The reaction product which is salted out with 70 parts of sodium chloride and filtered, is redissolved in 250 parts of water 6 3 Parts of 5-cyano-2,4,6-trichloropyrimidine are added at 0-5 and the mixture is stirred at this temperature for three hours Simultaneously, the p H is held at 8-8 5 by adding sodium car- bonate After the condensation is complete, the mixture is salted out with 45 parts of sodium chloride The dye precipitate is filtered by suction and then dried at 35 The dyestuff thus obtained correspond- ing to the formula _ SO 3 Na)25 Cu Pc SO 3 NaNH CHNH C 1 3 NHC Uh so 2 NH N 3 CN C 1 C 1 dyes cellulose fibres and particularly cotton a brilliant turquoise shade these dyeings have good light fastness and perfect wet fastness properties.

Example 474

If according to the method described in Example 473 the equivalent amount of the nickel phthalocyanine-dye base, i e 25 5 parts ( 0 025 mole) are used instead of 25 7 parts of the copper phthalocyanine-dye base, the corresponding lNi Pcl dyestuff (having the formula analogous to that of Example 473) is obtained which dyes cotton a bluish green shade The dyeings have good fastness properties.

Examples 475 to 480 By analogy with the method described in Examples 473 and 474 further phthalocyanine dyes may be prepared They correspond to formula (T 25) Case 150-5256 Me Pc - /-503 H)c ( 502 NH 2)d 23 R Ci S 2 SNH CK ( NliK N C 11 CN Cl in which the symbols are as defined in Table 25 below.

In the last column I the shade of each dyeing on cotton is given whereby T 25) e is and f is These dyeings brilliant turquoise bluish green.

have good fastness properties.

Table 25

Compounds of formula (T 25) Ex No Me c d R position -NH- Cu 3 0 H 2 1 H 1 2 4-503 H 2 1 2-COOH 2 1 H 1 2 4-503 H 3 3 H 3 -NHCH 2 CHNH- I CH 3 do.

do.

-NH(CH 2)3 N- CH 3 CH 3 475 476 477 478 479 480 Cu Cu Cu Ni Ni e e e e f f - I 81 - 150-5256 Example 481

25.5 Parts of the dye base, prepared in accordance with known methods by sulphochlorinating of nickel phthalocyanine and then reacting with 1,3-diaminobenzene-4-sulphonic acid, containing per molecule an average value of about 2 5 sulphonic acid groups and 1 sulphonamido group, in 150 parts of water are stirred with 1 8 parts of sodium nitrite This solution which is cooled to 0-2 , is added dropwise to 100 parts of an ice-water mixture and 12 parts of 30 % hydrochloric acid The resulting diazonium salt suspension is then added to a solution consisting of 5 9 parts of 1-( 3 '-methylamino- propyl)-6-hydroxy-4-methylpyridone-( 2) in 300 parts of ice/water, while keeping a temperature of 0-5 During coupling, the p H of the mixture is kept at 9-9 5 by adding a 30 % sodium hydroxide solution A green solution is obtained which is reacted with cyanuric chloride, followed by 1,2-diaminopropane and then 5-cyano-2,4,6-trichloropyrimidine, by analogy with the method described in Example 473, to obtain the dyestuff of the formula SO 3 Na) 25 Ni Pc 503 Na Ho1 O / C 1 CH 3 52 N N=N HO 7 CN C 1 (CH O \ 2 31 ON C 1 which is isolated in an analogous manner as described in Example 473.

The dyestuff dyes cellulose fibres and particularly cotton a brilliant green shade These dyeings have high light fastness and perfect wet fastness properties.

t 82 150-5256 Examples 482 to 519 By a method analogous to that described in Example 481 further phthalocyanine dyestuffs may be prepared They correspond to the formulae (T 26) and (T 27) So 3 H)2-3 Me Pc Me 5 "c \ R X N= CH 3 CN C 1 So 2 NH N=N 33 (T 26) B N -< NN 2 o I o-N 1 C 1 503 H) 2-3 Me Pc R R s 2 N=N / N "II 4 NIAN= X |NH </ N (T 27) R 12 W x, Cl CN C 1 in which the symbols are as defined in Tables 26 and 27 below.

The dyestuffs of Examples 482 to 519 dye cotton a green shade which is further brilliant when nickel phthalocyanine is applied.

These dyeings have notably good light and wet fastness properties.

< 83 - Case 150-5256 / Compounds Me R of formula (T 26) Q 3 -B 2-NR 1-(CH 2)3 N- I CH 3 do.

do.

-(CH 2)3 NH- -CH 2 CH 2 NH- do.

-(CH 2)3 NH- do.

-(CH 2)3 N- I CH 3 do.

do.

-CH 2 CH 2 NH- -(CH 2)3 N- I CH 3 do.

do.

-(CH 2)3 NH- -NHCH 2 CHNH- I CH 3 do.

do.

-NH(CH 2)3 N- I CH 3 do.

do.

-NHCH 2 CHCH 2 NH- OH do.

do.

-N N- \/ -NHCH 2 CH 2 NH- -Nr-CH 2 CH 2 NH- -NH(CH 2)3 NH- Table 26

Ex No.

482 483 484 485 486 487 488 489 490 491 492 493 494 495 496 497 498 Cu Ni Ni Ni Cu Ni Ni Ni Ni Ni Cu Ni Ni Ni Cu Ni Ni SO 3 H H H SO 3 H do.

do.

H SO 3 H do.

SO 3 H H SO 3 H do.

H H -CONH 2 H H H -CONH 2 H H H H -CONH 2 H H -CONH 2 H H Case 150-5256 Table 27 /

Compounds of formula (T 27) Ex.No Me R R 1 I R 12 Cu SO 3 H OH CH 3 Ni do.

Ni do.

Ni H Ni 503 H Cu do.

Ni do.

*Cu do.

Ni H OH NH 2 OH OH OH OH OH OH OH do.

do.

-COOH CH 3 do.

do.

-COOH CH 3 Ni H OH do.

Ni 503 H Cu do.

Ni do.

OH OH NH 2 do.

do.

Ni do OH do.

Cu do OH do.

H H H 2-SO 3 H H H 4 2-SO 3 H H H 2-SO 3 H do.

H 2-SO 3 H do.

do.

H 4 4 -NHCH 2 CHNH- I CH 3 do.

do.

-NH(CH 2)3 N- I CH 3 do.

do.

-NHCH 2 CHCH 2 NH- I OH do.

do.

-N N- -N NCH 2 CH 2 NH- -N NCH 2 CH 2 NH- \ / Ni H Cu H Ni SO 3 H Ni do.

Ni do.

OH OH OH NH 2 OH -COOR CH 3 do.

do.

H H H H 2-SO 3 H 4 4 -NHCH 2 CH 2 NH- do.

do.

-NH(CH 2)3 NH- 84 - R 9 position -NH- -v- 499 500 501 502 503 504 505 506 507 508 509 510 511 512 513 514 515 516 517 518 519 (k 150-5256 Example 520

By analogy with the method described in Example 481, using appro- priate starting compounds, the dyestuff of the formula so 3 Na)_ 2,5 Ni Pc SO 3 Na OH SO 3 H C 1 so 2 NH N= N I-| CH=CH SO 3 H NHCH CHN Hs,Cl 3 H 321 q CH)= 3 3 CN C 1 may be prepared and isolated It dyes cotton a brilliant green shade.

The dyeings obtained have good light and wet fastness properties.

In accordance with the method as described the dyestuffs of Examples 1 to 520 are obtained in sodium salt form They may, depend- ing on the reaction/isolation conditions or by reacting the sodium salts in accordance with known methods, also be obtained in free acid form or in other salt forms, for example those salt forms containing one or more cations indicated in the description above.

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

ky 86 150-5256 Application Example A 0.3 Parts of the dyestuff of Example 1 are dissolved in 300 parts of demineralised water and 15 parts of Glauber's salt (calcined) are added The dye bath is heated to 400, then 10 parts of cotton fabric (bleached) are added After 30 minutes at 400, 6 parts of sodium car- bonate (calcined) are 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 Subsequently, dyeing is effected for a further one hour at 40 .

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 parts of a commercially available anion-active detergent After rinsing with running hot water (for 3 minutes) and centrifuging, the dyeing is dried in a cabinet dryer at about 70 An orange cotton dyeing is obtained showing good light and wet fastness properties which are resistant to oxidative influences.

Application Example B To a dye bath containing in 300 parts of demineralised water parts of Glauber's salt (calcined), 10 parts of cotton fabric (bleached) are added The bath is heated to 400 within 10 minutes, and 0.5 parts of the dyestuff of Example 1 are added After a further 30 minutes at 40 3 parts of sodium carbonate (calcined) are added and dyeing is continued at 40 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 an orange cotton dyeing is ob- tained which has the same good fastness properties as indicated in Application Example A.

87 150-5256 Application Example C By a modified method as described in Application Example A, 0 3 parts of the dyestuff of Example 481 are used and instead of a total of 6 parts of sodium carbonate which are added portionwise, only 2 parts of calcined sodium carbonate are added in one portion The starting temperature of 40 is raised to 600, and dyeing is effected for a further one hour at 600 Otherwise, the method described in Application Example-A is employed analogously A brilliant green cotton dyeing of good build-up is obtained showing notably good light fastness properties.

Application Example D 2.5 Parts of the dyestuff of Example 473 are dissolved in 2000 parts of water 100 Parts of cotton fabric are added, and the tem- perature of the dye bath is raised to 800 within 10 minutes 100 Parts of Glauber's salt (calcined) are added and 30 minutes thereafter, 20 parts of sodium carbonate (calcined) Dyeing is continued for one hour at 800 Subsequently, the dyed fabric is rinsed with running cold, then hot water, and is washed at the boil according to the method given in Application Example A After rinsing and drying a brilliant turquoise cotton dyeing is obtained having good fastness properties.

Similarly, the dyestuffs of the remaining Examples or mixtures of the exemplified dyestuffs may be employed to dye cotton in accordance with the method described in Application Examples A to D.

Application Example E A printing paste consisting of parts of the dyestuff of Example 1 parts of urea 350 parts of water 500 parts of a 4 % sodium alginate thickener and 10 parts of sodium bicarbonate 1000 parts I 150-5256 is applied to cotton fabric in accordance with conventional printing methods.

The printed fabric is dried and fixed in steam at 102-104 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 An orange print is obtained which has good general fastness properties.

Similarly, the dyestuffs of Examples 2 to 520 or mixtures of the exemplified dyestuffs may be employed to print cotton in accordance with the method given in Application Example E All prints obtained show good fastness properties.

88 - 150-5256

Claims

Claims: -

1 A compound of formula I F - c C 1 a CN C 1 I b in free acid or salt form, in which Fc is the radical of a water-soluble azo, formazan, phthalo- cyanine, azomethine, oxazine, thiazine, phenazine or triphenylmethane dye which is in metal-free or metal complex form, which radical may contain a further fibre-reactive group, each a, independently, is O or 1 and b is 1 or 2; each X, independently, is a direct bond, -CO or -SO 2-, each R 1, independently, is hydrogen, unsubstituted C 1 _ 4 alkyl or Cl_ 14 alkyl which is monosubstituted by hydroxy, halogen, -SO 3 H, -O 503 H or -COOH, and each Alk, independently, is C 2 _ 4 alkylene; each W, independently, is N Bl - I R 1 -N C 2 _ 4 alkylene-N;_, I\/ R 1 N N(- N or (SO 3 H)M N- I A 1 -N N, /-N - -N N C 2 _ 4 alkylene N, k_ _ / I Al -NN -N N I (SO 3 H) in which 89 - - - - 150-5256 m is O or 1, and Bl is C 2 _ 6 alkylene, a C 2 _ 6 alkylene chain which is interrupted by -0 or -NR 1-, C 3 _ 6 alkylene which is substituted by one or two hydroxy groups or by one carboxy group, (CH 2)n (CH 2)n < or (CH 2)n,in which R 2 R 2 n is 0, 1, 2, 3 or 4, and R 2 is hydrogen, C 1 I-4 alkyl, C 1 _ 4 alkoxy, -COOH or -503 H, and mixtures of compounds of formula I.

2 A compound according to Claim 1, in which each R 1, indepen- dently, is hydrogen, methyl, ethyl, 2-hydroxyethyl, -(CH 2)r-503 H, -(CH 2)r-OSO 3 H or -(CH 2)q-COOH, in which r is 1 or 2 and q is 1, 2 or 3.

3 A compound according to Claim 1 or 2, in which each W, inde- pendently, is -N Blb-N or -N N in which I I \ l Rl b Rlb Blb is -C 2 _ 3 alkylene-, monohydroxy-substituted -(CH 2) - -C 3-4 alkylene, (CH 2)n or N 2 R 2 b R 2 b each Rib, independently, is hydrogen, methyl, ethyl or 2-hydroxyethyl, R 2 b is hydrogen or -503 H, and N 2 is 0, 1 or 2.

4 A compound according to Claim 3 in which each W, indepen- dently, is -NH-Blc-NH where B 1 is -C 2 _ 3 alkylene or monohydroxy- substituted -C 3 _ 4 alkylene.

91 - 150-5256 A metal-free compound ( 1) according to Claim 1 corresponding to the formula (Z)b KK in which DK KK ( 1) is the radical of a benzenic or naphthalenic diazo component, is the radical of a benzenic, naphthalenic or heterocyclic coupling component or of a CH-acidic compound capable of being enolised, Cl is N W C 1 CNC- CN CI in which W is as defined in Claim 1, and b is 1 whereby Z is bound to the diazo or coupling component by -N in which R 1 is as defined in Claim 1.

I R 1 6 A compound according to Claim 5 having the formula N KK 1 z a (la) in free acid or salt form, in which C 1 N i, Za is -</ N W 1 CN C CN Cl W 1 is -N B 1 i N- I I R 1 b Rib \ -N N-, N C 2 _ 3 alkylene -N N - \ I \ b R Ib z 92 - 150-5256 or -N N C 2 _ 3 alkyleneN- \-/ I Rib B 1, is -C 2 _ 4 alkylene, -C 2-_ 3 alkylene-0-C 2 _ 3 alkylene, -C 2 _ 3 alkylene N C 2-_ 3 alkylene-, I Rlb monohydroxy-substituted -C 3 _ 4 alkylene-, _o(CH 2)(CH 2)n R 2 a n 1 is 0, 1, 2 or 3, each Rib, independently, is hydrogen, methyl, ethyl or 2-hydroxyethyl, R 2 is hydrogen, methyl, methoxy, -COOH or -503 H; DK 1 is one of the groups (a 1) to (f 1) and (h 1) in which the ( 503 H) marked bond is attached to the azo group: - in which p is 0, 1 or 2, and Ra i each R 3 and R 4, independently, is hydrogen, chlorine, methyl, methoxy, ethoxy or -COOH; (al) in which m (SO 3 H) t R 5 a R 5 a O (CH 2) - (bl) (SO 3 H)m ( 503 H) (r 3)m (c 1) (SO H) 13 p / \ 4 a N- Rlb ( Rlb is O or 1, is 2 or 3, and is hydrogen, methyl, ethyl, -SO 3 H or 2-hydroxyethyl; in which m is O or 1, r is 1 or 2, and m + r are 2 or 3; in which Rlb, R 4, and p are as defined above; d 1) 93 - R Rlb -N CONH 4 (e) (SO 03 H)r (el 150-5256 R lb N NNHCO ( (SO 3 H)r (fl) in which Rib and r are as defined above; SO H / 3 (h 1) in which R 51 a is C 1 N - I Rlb (SO 03 H)r (SO 3 H)r 503 H or 2 S N H 9 CH 503 H a is O or 1, and R 50, Rlb and r are as defined above; and KK 1 is one of the groups (K 20), (K 3), (K 4) and (Ks) as defined below in which each marked carbon atom indicates the coupling posi- tion: - in which Ras is hydrogen, chlorine, methyl or methoxy, Rg 9 a is hydrogen, chlorine, methyl, methoxy, -SO 3 H or -COOH, and Rloa is hydrogen, -SO 3 H or -N-(Za); I Rlb (K 3) (K 2 a) 0 H N H _ O 0 H R 10 a 150-5256 R 8 a in which R 8 sa and Rg 9are as defined above, I N 9 Rga RI, is -OH or -NH 2, __I R 12 a is methyl, -COOH or -CONH 2, and N R 14 a R 14 is hydrogen, chlorine, methyl, ethyl, R 124 a -SO 3 H or -N-(Za); I (K 4) Rlb 2 Q 3 b in which Q 2is hydrogen, methyl, ethyl, phenyl, -COR 13, -CH 2 SO 3 H or -CH 205 03 H, HO O o+ Q 3 b is hydrogen, -CN, -SO 3 H, -C O R 13, Q 4 a methyl, ethyl, -CH 2 SO 3 H or -CH 2 NH 2, (Ks) each R 13, independently, is -OH, -0 C 1-4 alkyl or -NH 2, Q 4 a is hydrogen, -B 2 a -N-(Za), methyl, ethyl, cyclohexyl, phenyl Rlb or phenyl(Cl_ 2 alkyl), in which latter two groups the phenyl ring is unsubstituted or substituted by 1 or 2 substituents selected from chlorine, methyl, methoxy, -SO 3 H, -COOH, -NH 2 and -N-(Za), I Rlb or -C 1 _ 4 alkylene-Y 2, B 2 a is -C 2 _ 4 alkylene-, monohydroxy-substituted -C 3 _ 4 alkylene-, , -C 2 alkylene- -C-1 oc 12 alkylene or- (SO H) (SO 3 H ( 503 H ( 3)m( 3)m () in which m is as defined above, or B 2 a together with -N-(Za) to which it is attached, is I Rib -C 2 _ 3 alkylene -N N-(Za), Y 2 is -COOH, -SO 3 H, -O 503 H, -OH, -CN, methoxy or -NR 27 R 28, each R 27 and R 28, independently, is hydrogen; unsubstituted C 1 _ 4 alkyl; C 1.4 alkyl monosubstituted by hydroxy, C 1 _ 4 alkoxy, -COOH, -SO 3 H, -NH(C-14 alkyl) or N(Cl-4 alkyl)2; unsubstituted cyclohexyl; cyclohexyl 94 - I - 150-5256 substituted by 1 to 3 methyl groups; phenyl or phenyl(C 1 l_ 4 alkyl) in which each phenyl ring is unsubstituted or substituted by 1 or 2 substituents selected from halogen, preferably chlorine, C 1 _ 4 alkyl, C 1._ 4 alkoxy, -503 H and -COOH, or -NR 27 R 28 is a piperidine, morpholine or piperazine ring where each of these rings is unsubstituted or contains 1 to 3 methyl groups.

7 A compound according to Claim 5 or 6, having the formula R 7 a N-Z I a Rlb (lb) ( 503 H)r (SO 3 H)m in free < in which Rlb m r m+r R 6, R 7 a acid or salt form, and Za are as defined in Claim 6, is O or 1, is 1 or 2, and are 2 or 3, is hydrogen, methyl or methoxy, and is hydrogen, chlorine, methyl, methoxy, -NHCOCH 3 or -NHCONH 2.

8 A compound according to Claim 5 or 6, having the formula OH DK 2-N=N X 3 so 3 H (lc) in free acid or salt form, in which DK 2 is a group of formula (at), (b 1) or (c 1) as defined in Claim 6, and Rib and Za are as defined in Claim 6.

96 - 150-5256 9 A compound according to Claim 5 or 6, having the formula a DK 3 N = N SO 3 H a (ld) 503 H in free acid or salt form, in which each Rlb, independently, is as defined in Claim 6, Za is as defined in Claim 6, a is O or 1, the sulpho group is in the 3 or 4-position of the naphthyl ring, and DK 3 is a group of formula (a 2) or (c 2) SO 3 H 3 a R 4 a in which R 3 a and R 4 are as defined in Claim 6, (a 2) in which m is 0 or 1, p is 0, 1 or 2, and m + p are 1 or 2.

(c 2) 10 A metal-free compound according to Claim 1, having the formula R 6 R N-N N=N N-Z N N N< l Z( 2) R 7 R 7 x R 7 7 x ( 503 H)t k ' in free acid or salt form, in which C 1 Z is N/ N CN R 1 and W are as defined in Claim 1, t is 2 or 3, R 6 is hydrogen, C 1 _ 4 alkyl or C 1 _ 4 alkoxy, R 7 is hydrogen, halogen, C 1 _ 4 alkyl, C 1-4 alkoxy, or -NHC O NH 2, R 6 x, independently, has one of the significances R 7 x, independently, has one of the significances -NHCOC 1 _ alkyl of R 6, and of R 7.

metal complex according to Claim 1, based on the metal-free ( 3 a) or ( 3 b), OH NR 1 Z A N-=N 1 503 H (SO 3 H)m HO 3 S N -= NR Z ( 3 a) ( 3 b) 503 H in which Z is Cl w K <NC 1 CN C 1 97 - 150-5256 11 A compounds 98 - R 1 and V are as defined in Claim 1, A is H 035- 150-5256 or R 22 R 1 ( O H (SO 3 H)m (Rs 03 H) q ( 50 H) q R 17 ( 503 H)m each m, independently, is O or 1, q is 1, 2 or 3, R 17 is hydrogen, halogen, nitro, C 1 _ 4 alkyl, C 1 _ 4 alkoxy, -COR 13, -SO 3 H or -NHCOCH 3, R 22 is OH, OCH 3 or NH 2, and R 13 is OH, -OC 1 _ 4 alkyl or NH 2, which metal complex is in free acid or salt form, and is a 1:1 copper complex or a symmetrical or asymmetrical 1:2 chromium or 1:2 cobalt complex.

12 A 1:1 copper complex according to Claim 1, having one of the formulae ( 3 c) to ( 3 e), Cu" I R N N N ( 3 c) R.

N=N N Rj-z ( 3 d) ( 503 H)m (SO 3 H)r S ? 99 - SO 3 H Di N=N in free acid or salt form, in which Z is C 1 CN Cl N W CN C 1 R 1 and W are as defined in Claim 1, R 50 is hydrogen or 503 H, r is 1 or 2, m is O or 1, m+r are 2 or 3, R 2 is as defined in Claim 1, R 52 is hydrogen, C 1 _ 4 alkyl or C 1 _ 4 alkoxy, D 3 is SO H 1 3 or ( (SO 3 H)t t is 2 or 3, R 29 is hydrogen, COOH or 503 H, R 30 is hydrogen, C 1 _ 4 alkyl, C 1 _ 4 alkoxy or -0-Alk 1-0 R 5, Alk 1 is -C 2 _ 3 alkylene-, and R 5 is hydrogen, -503 H, C 1 _ 4 alkyl or C 2 _ 4 hydroxyalkyl.

I 150-5256 503 H Z ( 3 e) 150-5256 13 A metal-free compound according to Claim 1, having the formula H 2 N OH D -N=N N=N-D 1 2 SO O H 03 H 3 ( 4) l(CH 2) -NR 1-Zl l (CH 2)-NR"-Z lm in free acid or salt form, in which each Z, independently, is N_ 1 N -,c CN C 1 each R 1, independently, and W are as defined in Claim 1, each n, independently, is 0, 1, 2, 3 or 4, each m is O or 1 with the proviso that at least one m is 1, and each D 1 and D 2, independently, is the radical of a diazo component of the aminobenzene or aminonaphthalene series containing at least one sulpho, sulphonamido or carboxy group.

14 A compound according to Claim 1, having the formula /503 H) Me Pc ( 502 NR 24 R 25)d ( 7) 502 NR 2 _ (X R 4 a NR 1 Z R 2 in free acid or salt form, 26 in which c is 1, 2 or 3, and d is 0, 1 or 2, with the proviso that c + d do not exceed 3; - 150-5256 Cl CN Cl Z Cis N C 1 c N Cl each R 1, Pc Me each R 24 independently, and W are as defined in Claim 1; is the phthalocyanine radical, is copper, nickel, cobalt, iron or aluminium, and R 25, independently, is hydrogen or C 1 _ 6 alkyl, or -NR 24 R 25 is a saturated 5 or 6 membered heterocyclic ring which may contain one further -0 or -N in which I R 31 R 31 is hydrogen, C 1 _ 4 alkyl, 2-hydroxyethyl or 2-aminoethyl, R 26 is hydrogen, halogen, hydroxy, C 1 _ 4 alkyl, C 1 _ 4 alkoxy, -COOH or -SO 3 H, a is O or 1, X 4 is a divalent, optionally -N containing aliphatic, I R 1 araliphatic or heterocyclic bridging group, or is N= N KK 2, KK 2 is R i R (B 3)a R 12 3 a or B 2- B 2 R 11 R 12 R 13 R 9 in which each marked carbon atom indicates the coupling position, is -OH or -NH 2, is C 1 _ 4 alkyl or -COR 13, is -OH, -OC 1 _ 4 alkyl or -NH 2, is hydrogen, halogen, C 1 _ 4 alkyl, C 1 _ 4 alkoxy, -COOH or -SO 3 H, 41 i 101 - 150-5256 a is as defined above, B 3 is a divalent bridging group; Q 2 is hydrogen; C 1 4 alkyl; Cs_ 6 cycloalkyl; phenyl or phenyl- (C 1 _ 4 alkyl) in which each phenyl ring is unsubstituted or substituted by 1-3 substituents selected from C 1 x 4 alkyl, C 1 _ 4 alkoxy, halogen, -COOH and -SO 3 H; -COR 13 or C 1 _ 4 alkyl monosubstituted by -SO 3 H, -OSO 3 H or -COR 13, Q 3 is hydrogen; -CN; -SO 3 H; -COR 13; C 1 _ 4 alkyl; C 1 _ 4 alkyl monosubstituted by hydroxy, halogen, -CN, C 1 _ 4 alkoxy, _ R 9 R 9 -SO 3 H, -OSO 3 H or -NH 2; -502 NH 2; o/-i N R 15 or AN-e N) An 6, R 15 is hydrogen, C 1 _ 4 alkyl or C 2 _ 4 hydroxyalkyl, Ane is a non-chromophoric anion, R 9 and R 13 are as defined above, B 2 is C 2 _ 6 alkylene, monohydroxy-substituted C 3 _ 6 alkylene, a C 2 _ 6 alkylene chain which is interrupted by -0 or -NR 1-, or (SO 3 H) -Cl_ 4 alkylene (SO 3 H)m C 1-4 alkylene- ( 503 H) 3 m in which R 1 and m are as defined in Claim 1, or -B 2 NR 1 (Z) is -C 2 _ 4 alkyleneN N (Z), and mixtures of compounds ( 7).

102 - -103 150-5256 A compound defined in Claim 1, substantially as herein described with reference to any one of Examples 1 to 520.

16 A process for the preparation of a compound of formula I, defined in Claim 1, and mixtures thereof, comprising reacting a com- pound of formula II C 1 F X No-Alk N / XN I I l1 y 3 II a 3 b in which Y 3 is -W H or chlorine, and F, X, R 1, -Alk-, a, b and W are as defined in Claim 1, or a mixture of compounds of formula II, if Y 3 is -W H, with 5-cyano-2,4,6-trichloropyrimidine, or, if Y 3 is chlorine, with a compound of formula III H-W XC 1 N III CN C 1 in which W is as defined above, using a 1:1 molar ratio for the compounds of formulae II and III.

17 A process for the preparation of a compound of formula I, defined in Claim 1, substantially as herein described with reference to any one of Examples 1 to 520.

18 A compound of formula I, defined in Claim 1, whenever obtained by a process according to Claim 16 or 17.

19 A process for dyeing or printing hydroxy group or nitrogen- containing organic substrates comprising applying to the substrate a compound of formula I or a mixture thereof defined in Claim 1, as dyeing or printing agent.

104 150-5256 A process according to Claim 19, wherein the substrate is a fibre material containing or consisting of natural or regenerated cellulose.

21 A process according to Claim 20, wherein the substrate is a textile material containing or consisting of cotton.

22 Dyed or printed substrates whenever obtained by a process according to any one of Claims 19 to 21.

23 A process for dyeing or printing a substrate substantially as herein described with reference to any one of application Examples A to E.

Published 1989 at The Patent Office, State Rouse, 66 '71 High Holborn, London W Cl R 4 TP Further copies maybe obtainedfrom The Patent Office.

Sales Branch, St Mary Cray, Orpington, Kent BR 5 31 D Printed by Multiplex techniques ltd St Mary Cray, Kent, Con 1/87