FR2632651A1 - NOVEL TRIAZINIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS REACTIVE DYES - Google Patents

Abstract

The subject of the invention is the compounds of formula (CF DRAWING IN BOPI) in which Fc signifies the residue of a water-soluble dye chosen from azo dyes, formazan, phthalocyanine, azomethine, oxazine, thiazine, phenazine and triphenylmethane, in non-metallized or metallized form, said residue possibly also containing a reactive group, and the other symbols have various meanings. These compounds and their mixtures are useful as reactive dyes for dyeing or printing organic substrates containing hydroxy groups or nitrogen.

Description

The present invention aims at new

  triazin compounds and their process for preparing

  tion. These compounds are suitable for use

as reactive dyes.

  The invention more particularly relates to the compounds of formula I Ci -N-Alk c to P CN C1l-b in which

  Fc means the remainder of a hydrosoluble dye

  selected from azo dyes, from

  formazane-, phthalocyanine, azo

  methine, oxazine, thiazine, phenazine and triphenylmethane, in non-metallized or metallized form, said residue may also contain a reactive group, each a means, independently, 0 or 1, b means 1 or 2 each X independently means a direct bond, -CO- or -SO 2 -, each RI independently means hydrogen or an unsubstituted or monosubstituted C1-C4 alkyl group by a halogen or hydroxy group; SO3H, -OSO3H or COOH,

  each Alk independently means an alkyl group

  in C2-C4, and each W independently means a remainder

-N-B1-N-, -N N-

RI

R1 R1

  -N- (C 2 -C 4) alkylene-N- (C 1 -C 4) -N-N-alkylene-1-, R 1 -N or -N IN R 1 = R 1

(SO3H) (SO3H)

where m is 0 or 1 and

  B1 is a C2-C6 alkylene group, optionally

  optionally interrupted by -O- or -NR1-, a C3-C6 alkylene group which is substituted by one or two hydroxy groups or a carboxy group, or a residue

- (CH2) nV OR S (CCH2) n-

- (CH2). or

R2 R2

  wherein n is 0, 1, 2, 3 or 4 and R 2 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, -COOH or -SO 3 H, and mixtures of compounds of formula I,

  in free acid form or in salt form.

  In the present application, any alkyl, alkenyl, alkynyl or alkylene group present is linear or branched unless otherwise indicated. In the hydroxy-substituted alkyl or alkylene groups attached to a nitrogen atom, the hydroxy group is preferably bonded to a carbon atom which is not attached directly to the nitrogen atom. In the alkylene groups containing 2 hydroxy groups, the hydroxy groups are bonded to different carbon atoms which preferably are not adjacent to each other.

  compared to each other. In the alkylene groups

  broken by -O- or -NR1i and attached to a nitrogen atom, -O-

  or -NR1-is preferably bonded to a carbon atom which

  is not attached directly to the nitrogen atom.

  Halogen is preferably fluorine, chlorine or bromine; it is more preferably

  chlorine or bromine, especially chlorine.

  F. preferably means a water-soluble residue of a monoazo or disazo dye

  non-metallized or metallized which, when

  is preferably a 1: 1 copper complex, a 1: 2 chromium complex or a 1: 2 cobalt complex, or the water-soluble residue of a formazane dye,

  from phthalocyanine to copper or nickel or

triphènedioxazine.

  Preferably, each X preferably means

  independently, a direct bond or -SO2-.

  Preferably, each Alk preferably means

  independently, a C2-C3 alkylene group.

  Any alkyl group represented by R 1 preferably contains 1 or 2 carbon atoms. Any substituted alkyl group represented by R 1 means

  preferably a C 1 -C 3 alkyl group containing

  a substituent selected from a hydroxy group,

  -SO3H, -OSO3H and -COOH, especially a hydro-

  xy. Each R1 preferably means R1, each R1a being, independently, hydrogen, methyl, ethyl, 2-hydroxyethyl, - (CH2) r-SO3H, - (CH2) r -SOO3H or - (CH2) q- COOH, in which r stands for

i or 2 and q means 1, 2 or 3.

  Each R1 is more preferably R1b, with each Rib meaning, independently, hydrogen or a methyl, ethyl or 2-hydroxyethyl group. Each R1

  Especially means hydrogen.

  Each R2 preferably signifies R2, each R2. meaning, independently, hydrogen or a methyl, methoxy, -COOH or -SO3H group. Every R2

  means more preferably R2b, each R2b signifies

  independently, hydrogen or -SO3H.

  Each B1 preferably means Bi, each B1. meaning, independently, a C 2 -C 4 alkylene, - (C 2 -C 3) alkylene-O (C 2 -C 3) alkylene -, - (C 2 -C 3) alkylene-N- (C 2 -C 3) alkylene - R1b C3-C4 alkylene monosubstituted with a hydroxy group, - (CH2) n CH) or R2a R2a

o n1 means 0, 1, 2 or 3.

  Each Bi means more preferably Bib,

  each B1b meaning, independently, an alkyl group

  C2-C3 alkene, C3-C4 alkylene monosubstituted with a hydroxy group,

(CH2) -

- (CH2) n OR or n2 R R2b R2b

o n2 means 0, 1 or 2.

  Each B1 signifies especially B1c, each BI signifying, independently, a C2-C3 alkylene group, or C3-C4 alkylene monosubstituted with a hydroxy group. Each W preferably denotes W1, each W1 meaning, independently, a residue R -N-Bla-N-, -N N-, -N @ lkylene C2-C3-N- OR Rlb Rlb Rlb

-N N -alkylene C2-C- -N-

  Rlb Each W means more preferably W2, each W2 meaning, independently, a remainder

-N-Bib- N- Or -N N-

  Rlb Rlb W especially means W3, each W3 meaning,

independently, -NH-B1 -NH-.

  The preferred compounds of formula I in non-metallized or metallized form correspond to the compounds of formulas (1) to (7) as defined below: Compounds of formula (1) (Z) b

LDK - N = NKK Z (1)

  wherein DK means the remainder of a benzene or naphthalenic diazotization component, KK means the remainder of a benzene, naphthalenic or heterocyclic coupling component, or the remainder of an acidic CH compound capable of being enolized, Z means CN ci CN Cl o W is as defined above, and b is 1 or 2, one or two groups Z being linked to the component of

  diazotation and / or coupling by a group -N (R1) -.

  b is preferably 1, in a compound of formula (1), DK preferably means one of the following groups (a) to (h) in which each bond marked with an asterisk is attached to the azo group,

R2 (SO 3H)

  2R3 p / R3 R R 50-Alk-O (SO 3H) q R4 (a) (b) -N

R CON *

R 1

(S03H)

4 (C2) N r (e) (d) R1 (e)

R R

  nCO (SO 3) r (SO 3 H) r (f) (g) soH ci

- N5 N

  (H) Ri '= <and where R 1 and R 2 are as defined above, R 3 is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, acetylamino, benzoylamino; 503H or -COR13, R4 is hydrogen, halo or C1-C4alkyl, C1-C4alkoxy or -COR13, R13 is -OH, -O-C1-C4alkyl or -NH2, Alk1 is C2-C3 alkylene, R5 is hydrogen, -SO3H, C1-C4alkyl or C2-C4hydroxyalkyl, Rs50 is hydrogen or -SO3H, R51 is -SO (SO3U) Hp RR ( S03H) q or N

CH R

  CH3 R1 S03H n is 0, 1, 2, 3 or 4, p is 0, i or 2, q is 1, 2 or 3, and r is 1 or 2, KK is preferably one of the groups (K1 ) to (KR) in which the carbon atom marked with an asterisk indicates the position where copulation occurs, R.6

9 N - - (K1)

R

R 1

  wherein R 1 is as defined above, R 6 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, and R 7 is hydrogen, halogen or C 1 -C 4 alkyl, alkoxy C1-C4, -NHCO-C1-C4alkyl or -NHCONHZ, R8

- K8

COCH j R

1, 9

  wherein R 1 is as defined above, R 8 is hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy; R 8 is R 2 hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, -COOH or -SO 3 H, and R 10 is hydrogen, -SO 3 H or -NR 1 - (Z), E 65

0 H

ON ^

> "0 (K3)

N 0 H Rll

ÀN_ -Q1

  wherein R1 is -OH or -NH2, R12 is C1-C4alkyl or -COR13, R13 is as defined above. Q .: means hydrogen, C1-C4alkyl -C4 or R8 R9 R14 R8 and R9 are as defined above, and R14 is hydrogen, halogen or C1-C4 alkyl,

-CON C 8

R1 R

  R9 -SO3H or - (B3), - N- (Z) o R1 and a are as R1 as defined above and B3 is a divalent bridge group, 11 Q2 - 3 HO N (Ks) Q4 wherein Q2 means hydrogen, a C 1 -C 4 alkyl group, a C 5 -C 6 cycloalkyl group, a

  phenyl or phenylC 1 -C 4 alkyl in.

  which the phenyl ring carries

  from 1 to 3 substituents selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, -COOH and -SO 3 H, a group

  -COR13 or a mono-C1-C4 alkyl group

  substituted with -SO3H, -OSO3H or -COR13, Q3 is hydrogen, -CN, -SO3H, -COR13, C1-C4 alkyl, C1-C4 alkyl monosubstituted with halogen or by

OH, CN, C1-C4 alkoxy ,.

  R - <Rg, -SO3H, -OSO3H - or --NH2, D or a group SO2NH2,

R- R '

9 '15

  Embedded image wherein R 15 is hydrogen, C 1 -C 4 alkyl or C 2 -C 4 hydroxyalkyl, and AnG is a non-chromophoric anion, Q 4 is hydrogen, a -B 2 -N- (Z), C1-C6 alkyl, R1

  C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, cycloalkyl

  C 5 -C 6 alkyl, phenyl or phenyl-C 1 -C 4 alkyl in which the phenyl ring optionally carries from 1 to 3 substituents selected from halogen and C 1 -C 4 alkyl, C 1 -C 4 alkoxy, -SO 3 H, -COOH and -N- (Z), or a - (C 1 -C 6 alkylene) -Y R 1 group in which Y signifies -COOH, -COO-C 1 -C 4 alkyl, -SO 3 H, -OSO 3 H, -OH , -CN, C1-C4 alkoxy, -NH2 or an aliphatic amino group,

  cycloaliphatic, aromatic or heterocyclic

  protonable clique or a quaternary ammonium group, and

  B2 is a C2-C6 alkylene group,

  C3-C6 monosubstituted by a hydroxy group, a C2-C6 alkylene group which is interrupted by -O- or -NR1-, or a residue (C1-C4 alkyl);

(S H) (SO H)

M 3 m

C1-C4 alkylene -

(S03H)

  or B2-NR1- (Z) is - (C2-C4 alkylene) -N N- (Z), and R1, R8, R10 and R13 are as defined above, NR OH NLR1CO * \ Ja (K6)

S03H.-

(S03H) m

- OH NHCOR16

(K7) Q H

S3. (S03H) -

  wherein R 16 is C 1 -C 4 alkyl, phenyl or phenyl having 1 to 3 substituents selected from halogen and C 1 -C 4 alkyl and C 1 -C 4 alkoxy, and

  R1, a and m are as defined above.

Compounds of formula (2)

-R R

6 x

N = N 'N N' N-Z

(s 3H) t

R (2)

R7 R 1

  7x (S031 t wherein R6, R7, R1 and Z are as defined above, t is 2 or 3,

  R6x independently of R6 has one of the significant

tions of R6 and

  R7x independently of R7 has one of the

R7.

  The preferred compounds of formula (2) are those wherein R6, R6, X and R7, X are as defined in US Pat. aTTu6bTs LIE

(H OS) BED

  nvq snLd sLuEJp. anb -eLa; uos b 1a w no- 'S OH b (H OS) m (Húos)

H L

naT; eTuBTs v

Z CC

  2neq snld sTuT; gp anb sial quos m ie z 'Z T slanbseT suep T H OS (qi) - E H OSXN = N so HEs - NN S OH HS HO Zd

(H OS) HEOS

tN -) N = N-Y

Z_-EN HO

sIu2ATns sS TT uW uou.

  (qE) no (eu) ainuo; ap sesodwoD saT ans saseq 'ITeqoz do not no aWo1qa do Z: T saxaldmoo saT; aAmnD ne T: T saxaTdwoz saToueala:; d ee' tthee tthee tttee ssdddddddd a2TD qned uo '(ú) aInmao ap sasodmoD aumoD aeuBo60pAq , T LS99Z bT l S 9 zú9 Z

-SO3H or -NHCOCH3, -

R22 is OH, OCH3 or NH2, and

R13 is as defined above.

  In a 1: 2 chromium or cobalt complex, the 2 azo radicals are identical or different, i.e., it is a 1: 2 metalliferous complex.

symmetrical or asymmetrical.

  The 1: 1 copper complexes particularly

  Most preferred are those based on a compound of formula (3a) wherein A is the remainder of a benzene diazotisation component and the remainder of the naphthalenic coupling component is OH

- s.

SO3H NR-Z

  As other compounds of formula (3), there may be mentioned in addition the 1: 1 cupric complexes corresponding to the following formulas (3c) to (3e) OCu O

0- NN 0

  Wherein Rso0 is hydrogen or SO3H, and R1, Z and r are as defined above, Cu R - o R- N-N N (3d)

R. R (SO H) (SO 3H)

  Wherein Rs2 is hydrogen or C1-C4alkyl or C1-C4alkoxy, m is 0 or 1, r is 1 or 2 and m + r is 2 or 3, and R1, R2, Rso and Z are as defined above, Cu

0, 0 S0 H

3 (3rd)

D3- N = N / N-N

R52 SOH

  wherein D3 is H2R29 is hydrogen, COOH or SO3H, R30 is hydrogen, C1-C4alkyl, C1-C4alkoxy or -O-Alk11-OR5, and t, R5 and Alk1 are as defined above, and

  R1, R52 and Z are as defined above.

Compounds of formula (4)

H N OH

D1-N = N H N-N-D (4)

  Where each D1 and D2 independently means the remainder of a diazotizing component of the series of

  aminobenzene or aminonaphthalene,

  at least one sulpho, sulphonamido or carboxy group, each m is 0 or 1, with the proviso that at least one symbol m means 1 and R1, Z and n are

as defined above.

  D1 preferably denotes D1 ,, D1, signifying a group of formula (ax) or (cx) R18 D R19 R4 (SO3H) p (SO3H) m '(a) in which R18 signifies a sulpho, sulphonamido group. or -COR13, R19 means hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, -NHCOCH3 or

SO3 H,

  R13 m and p are as defined above, and

m + p means 1 or 2.

  D2 preferably means D2a, D2a means

  By leaving a group of the formula (d.) R 2 18 * / \ (dx) R 4 wherein R 4 and R 11 are as defined above, the bond marked with an asterisk is attached to the azo group and the other free bond is fixed at

reactive group.

  In group (dx), R18 is located more

  in position 2 (with the azo group in position

  1) and the free link which is fixed to the group

  reagent is located in position 4 or 5.

  Compounds of formula (5) NR1-Z (H03S) (Cu t

N N

1 (S03H) M (5) NcN (S03H) p

R20 R21

  wherein one of the symbols X1 and X2 means -O- and the other signifies a carboxy group,

  each R20 and R21 independently means the hydro-

  C 1 -C 4 alkyl, C 1 -C 4 alkoxy, -COR 13 or -NHCO (C 1 -C 4 alkyl) gene, R 1, R 13, Z and m are as defined above, each p means, independently, 0, 1 or 2 and

m + 2p means at least 2.

  Compounds of formula (6) ## STR5 # , independently, hydrogen or

-S02 CH2CH2 0S03H,

  each m means, independently, 0 or 1 ,.

  each X3 is, independently, -SO2-, -NR1-, -CONR1-, or -SO2NR1, in which the atom marked with an asterisk is attached to a carbon atom of the ring,

  each Alk2 independently means an alkyl group

  C2-C4 and each R1 and Z, independently, is as defined above,

  and mixtures of compounds of formula (6).

  In the compounds of formula (6), the 2

  Z symbols are preferably identical.

  Compounds of Formula (7) ## STR5 ## wherein R is 1, 2 or 3, and d is 0. , 1 or 2, with the proviso that c + d is not greater than 3, Pc means the remainder of phthalocyanine, Me means copper, nickel, cobalt, iron or aluminum,

  each R24 and R2s independently means hydrogen.

  C1-C6alkyl or -NR24R25 is a 5- or 6-membered saturated heterocycle which may further contain -O- or -N (R31) - where R31 is hydrogen

  or a C1-C4 alkyl, 2-hydroxy-

  ethyl or 2-aminoethyl, R26 is hydrogen, halogen or hydroxy, C1-C4 alkyl, C1-C4 alkoxy, -COOH or -SO3H, a is 0 or 1,

  X4 means a divalent aliphatic bridge, arable

  lipase or heterocyclic, said bridge optionally containing -N (R1) -, or means -N-N-KK2 wherein KK2 means

R1 R Q2

t1 | orA

N (B3) - HO O

  R 1, R 11, R 12, R 12, Q 2, -B 2 -, -B 3 - and a are as defined above, the carbon atom

  marked with an asterisk indicating the posi-

  where coupling is effected, Q3a is hydrogen, -CN, -SO3H, -COR13, C1-C4alkyl, C1-C4alkyl monosubstituted with halogen or hydroxy, -CNalkoxy C-C4, -9 -S3H, -OS03H or -NH2, or a group -SO2NH2y t or C Ane, wherein Rg, R13, R15 and AnQ are as defined above,

  and mixtures of compounds of formula (7).

  The reactive group Z preferably means a group Za corresponding to the formula C1 No

tW - Z ..

CN Cl

  z more preferably means Zb, Zb means

  leaving a group Za in which W1 is W2. It especially signifies Zó, Zc signifying a group Za in which W1 is W3. The preferred compounds of formula (1) are those corresponding to the following formulas (la) to (ld). Compounds of formula (la) za DK1-N-N KK1 (la) wherein Za 'is as defined above and is attached to DK1 or KK1, DK1 means one of the following residues (a1) to (f1) and (h1) in which the labeled bond of a asterisk is fixed to the azo group,

(SO3H)

  (a) R4R R3a where p is 0, 1 or 2, and

  each R3. and R4. means, independently, the hydro-

  gene, chlorine or a methyl group, methoxy,

ethoxy or -COOH, -

  (S03H) (b1), (b1) R5aO (CH2) -Ol0 is 0 or 1, t is 2 or 3, and Rs5a is hydrogen or methyl, ethyl, -SO3H or 2-hydroxyethyl, (cl) ( S03H) r (SO3H) mom means 0 or 1, r is 1 or 2, and m + r is 2 or 3,

(SO H)

13 p

(d1) R4a N-

  Rlb o Rlb, R4a and p are as defined above,

R R

  ## STR2 ## where R 1 and R 1 are as defined above, SO H R 5 N / R 51a (h 1) 0 -Di N

C l NH-

  C1 o Rslas means N (SO3H) r (SOH) SQ3H R R50 N

or and.

  CH3 S03H R5o, R1b, a and r are as defined above, and KK1 means a remainder (K3) as defined above, or one of the following residues (K2a), (K4) and (K5,) R8 o R8. means hydrogen,

  COCH3 R9a chlorine or a methyl or methyl group

  CC3 'R9a -CHCOXH thoxy, Rg. means hydrogen, chlorine R10Oa or methyl, methoxy, -SO3H (K28) or -COOH, and RoO. is hydrogen, -SO3H or -N- (Z,), R1, R11, R8s and Rg, are as defined above, R7Ra R12, methyl, N1, TCOOH or -CONH 2, and NR 1 R 14, signifies hydrogen, chlorine D 14a 212a or a methyl, ethyl, -SO 3 H (K 4) or -N- (Za) group, R 1 b Q 2a o Q 2a signifies hydrogen or Q3b is methyl, ethyl, phenyl, HO-Q3b COR13, -CH2SO3H or -CH2OSO3H, NHOO Q3b is hydrogen or Q4a -CN, -SO3H, -COR13, methyl, (K5s) ethyl, - CH2SO3H or -CH2NH2, Q4, means hydrogen, -B2a-N- (Za), an IR group b methyl, ethyl, cyclohexyl, phenyl or phenyl-alkyl

  C1-C2 in which the phenyl ring carries

  1 or 2 substituents selected from chlorine and methyl, methoxy, -SO3H, -COOH, -NH2 and -N- (Za), R b or a - (C1-C4 alkylene) -Y2, B2a group means a C2-C4 alkylene group, alkylene in

2632-651

* C3-C4 monosubstituted by a hydroxy group, or a residue

C1-C2 alkylene) -

  or - (C 1 -C 2 alkylene)) or (SO 3 m (SO 3 OH) (SO 3 H) m

  or B2a, together with -N- (Z,) to which it is attached,

  R 1 b is -CO (C 2 -C 3 alkylene) -N-N- (Z 2), Y 2 is -COOH, -SO 3 H, -OSO 3 H, -OH, -CN,

  methoxy or -NR27R28, each symbol R27 and R28 signifies

  independently, hydrogen; a substituted C 1 -C 4 alkyl group; a C 1 -C 4 alkyl group monosubstituted with hydroxy, C 1 -C 4 alkoxy, -COOH, -SO 3 H, -NH-C 1 -C 4 alkyl or-N- (C 1 -C 4) alkyl 2; a group

  unsubstituted cyclohexyl; a cyclohexyl group

  stituted with 1 to 3 methyl groups; a phenyl or phenyl-C 1 -C 4 alkyl group in which the phenyl ring optionally carries 1 or 2 substituents chosen from halogens, preferably chlorine, and C 1 -C 4 alkyl, C 1 -C 4 alkoxy, -SO 3 H and -COOH, or -NR2. R28 is a piperidine, morpholine or piperazine ring, each of which is unsubstituted or contains from 1 to 3 methyl groups; The compounds of formula (Ib) R 6a

N N N-Z

  1a (Ib) R7a R1b (SO3H) r (SO3H) m wherein m + r is 2 or 3, R6. means hydrogen or methyl or methoxy and R7 is hydrogen, chlorine or methyl, methoxy, -NHCOCH3 or NHCONH2; The compounds of formula (Ic) ## STR2 ## in which DK2 denotes a group of formula (a,), (b1) or (ci) as defined above; The compounds of formula (Id) OH NRlbGO 5 lb t Ob H4, Cox DK-N = N a 33 (1d)

SO3H SOH

  wherein the sulfo group is in the 3 or 4 position of the naphthalene ring, and DR3 is a group of formula (a2) or (c2)

263'265 1

  Wherein R3a and R4 are R4 as defined above, 3a R4a (a2) (SO3) (S3) wherein m + p is 1 (SO3H) p (SO3H) m

3P 3 M or 2.

  (c2) The preferred compounds of formula (2) are those corresponding to formula (2a)

N --- N N NN - Z

  wherein R7a is as defined above and m + r

means 2 or 3.

  The preferred compounds of formula (3) are the 1: 1 cupric complexes, based on the non-metallized compounds of formula (3al) or (3bl) OH A 17 N = N: (3al) So H NZ 3 1 a R 1b in which A1 R22a R22a R17a 4 or SO H (SO3H) r (SO3H) m 03H R17a means hydrogen, chlorine, bromine or a nitro, methyl, methoxy, -SO3H or -COOH group, R22a means OH or OCH3 and m + r means 2 or 3,

R22 OH NH2

HOS NN S03H

3 -

"- (3bj) S03H N-Z I a Rlb

  O R22a is as defined above.

  Other preferred compounds of formula (3) are the 1: 1 cupric complexes corresponding to the following formulas (3c1), (3dj) and (3e1), Cu 0o 'o0 (SOH) J./J. 3m

XN = N X N.

R A (3%)

/ -H S03H SORH

N-Z S03H 3

I a lb Cu R2 2a, 0

N = N N - -

R,> NN (3dl)

R50 N-Z R (0H)

0 to z52a SO H3 r R1b / Cu_

O so3.

D3 - N = N - = N = N - (3ei)

H RN-Z

  R52a S0H has 3 Ribs wherein R50 and R2 are as defined above, R52. means hydrogen or a methyl or methoxy group and SO3H D3. means R 29 R a O R30. means hydrogen or a methyl or methoxy group. The preferred compounds of formula (4) are those of formula (4a), R1

H2N OH 2

  D -N N N = N 4 (4a) la (4a) - N-Z R I a

SO3H 4 R

  SO3H 3 lb $ 3H wherein D1, R4 and R1 are as defined above; the compounds which are particularly preferred are those of formula (4a) in which R4 signifies hydrogen and R18 is located in position 2 and N-Z1 is located in Rlb

position 4 or 5 of the phenyl group.

  Preferred compounds of formula (5) are those in which each R 20 and R 21 is R 20a and R 21a, each R 201 and R 21, independently, being hydrogen, chlorine or a methyl, methoxy group,

-COOH or -NHCOCH3.

  The preferred compounds of formula (6) are those wherein Q is O-, each X3 independently means -N (R1b) - or - * SO2N (Rib) -, each R1 independently means R1b,

  each Alk2 independently means an alkyl group

in C2-C3, and

  each Z means, independently, Z ..

  The compounds of formula (6) which are particularly preferred are those in which the two groups

containing Z. are identical.

  Preferred compounds of formula (7) are those in which Me means copper or nickel, and

  each R24 and R25 signifies hydrogen.

  The compounds of formula (7) which are particularly preferred are those in which Me means copper or nickel, c is 2 or 3 and d is O, each R 1 independently means R 1b Z means Za, R 26 means hydrogen, COOH or -SO3H and either a is 0, or a is 1 and X4 is -NN-KK2 where KK2 is a residue Q2a H0 i Q3b 2a- where Q2, Q3b and -B2 are such that

defined above.

  In addition, it is particularly preferred that in all the above-mentioned nonmetallized compounds and metalliferous complexes (1) Za is Zb, (2) -Za is Z:

  (3) Za means Zó and Rlb means hydrogen.

  When a compound of formula I is in salt form, the cation associated with the sulfo groups and any carboxy group is not critical and may be any non-chromophore cation usual in the field of reactive dyes provided that

  the corresponding salts are soluble in water.

  Examples of such cations are alkali metal cations and unsubstituted or substituted ammonium cation, for example cations.

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

  and tetramethylammonium, triethylammonium and mono-, di-

and tri-ethanolammonium.

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

  being particularly preferred.

  In a compound of formula I, the cations of the sulfo group and any carboxy group may be the same or different, for example a mixture of the aforementioned cations, which means that the compound of formula I may be in the form of a

mixed salt.

  The present invention also relates to a process for preparing compounds of formula I and mixtures of compounds of formula I, wherein a compound of formula II is reacted

F X-N-A1k 1 ---

  Wherein Y 3 is chlorine or -W-H, and F 1, X 1, R 1, Alk, a, b and W are as defined above, or a mixture of compounds of formula II,

  when Y3 signifies -W-H, with 5-cyano-2,4,6-tri-

  chloropyrimidine or, when Y3 signifies chlorine, with a compound of formula III H-W ci

> N III

  CN C1 wherein W is as defined above, using a 1: 1 molar ratio for the compounds

of formula II and III.

  In a compound of formula II, Y3 preferably means -W-H. The condensation reaction of a compound of formula II wherein Y 3 is - WH with 5-cyano-2,4,6-trichloropyrimidine is suitably carried out at a temperature of 0 to 40 ° C and at a pH of between 7 and 9. As a reaction medium, water is normally used, but

  can also use 5-cyano-2,4,6-trichloro-

  pyrimidine dissolved in an organic solvent, by

example in acetone. The dieazoic compounds of formula (4) can also be obtained

  by diazotisation of a compound of formula IV wherein D2, R1, Z, m and n are as defined above, and alkaline coupling with a compound of formula V ## STR2 ##

H N OH

D1 - N = N;

  ## STR5 ## wherein D 1, R 1, Z 2, m and n are as defined

upper.

  The compounds of formula I can be isolated by known methods, for example by salting out with an alkali metal salt, filtration and drying.

  possibly under vacuum and at light temperatures.

high.

  Depending on the reaction and isolation conditions, the compound of formula I is obtained in free acid form or preferably in the form of a salt or even in the form of a mixed salt, for example containing one or more of the cations mentioned above. . The compound of formula I in free acid form can be converted into salt or mixed salt or vice versa; the salts can be transformed according to the methods

known in other salts.

  The starting materials of formulas II, III, IV and V are known or can be prepared according to known methods using known starting materials. The compounds of formula I and mixtures thereof are useful as reactive dyes for dyeing or printing organic substrates containing hydroxy groups or nitrogen. The preferred substrates are leather and fibrous materials consisting, in whole or in part, of natural or synthetic polyamides and in particular of natural cellulose

  regenerated, such as cotton, viscose and

  branne. Particularly preferred substrates are

  those made, in whole or in part, of cotton.

  The dyeing or printing is carried out according to methods known and customary in the field of reactive dyes. For the compounds of formula I,

  the process of exhaustion dyeing is carried out

  preferably at temperatures between 30 and C. The compounds of the invention are fully compatible with other reactive dyes; they can be applied alone or in combination with suitable reactive dyes of the same class having similar dyeing properties, for example as regards the usual fastnesses and the climbing power on the fibers, etc. The dyes obtained

  with such associations have good

  are comparable to those obtained with the

dye alone.

  Because of their power to rise remarkably

  quable, the compounds of formula I give

  exhaustion and excellent fixation yields.

  The unbound dyestuff portion can be easily removed from the substrate by washing. The dyes and prints obtained have good fastness to dry and wet light and also good wet fastness, for example washing, water,

  sea water and perspiration. They are resistant

  oxidation, for example chlorinated water, hypochlorite bleaching and

  containing peroxides or perborates.

  The following examples illustrate the present invention without in any way limiting its scope. In these examples, parts and percentages are by weight or volume and temperatures are

in degrees Celsius.

Example 1

  1.8.3 parts (0.025 mole) of the compound of formula B SO3H Ci

N H

N = N (BH> N <

S3OH S03H NHCOCH CHNH

3 3H NHCH2 21 2

  CH3 in 500 parts of water is added in one go to 250

  6.1 parts solution (20% excess) of 5-cyano-2,4,6-

  trichloropyrimidine-in acetone. The reaction mixture pH which drops spontaneously is maintained at 7 - 7.5 by continuous addition of a 20% solution of sodium carbonate.

  sodium. The mixture is heated at the same time to reach

  to a final temperature of 35. After 3 to 4 hours, the condensation is complete (checked by chromatography

thin layer).

  To isolate the reaction product, the resulting solution is heated to a dull red-orange and stirred with filtering soil for about 10 minutes. The mixture is then filtered to obtain

  a clear solution and added to the filtrate, under stirring.

  sodium chloride (about 10% by volume). The

  Fine precipitate is filtered and dried at about 50 under vacuum.

The compound of formula is obtained

N = N NH N

-OJHSO3HNHCONH2 NHCH3 t

CN C1

  which dyes the cotton in an orange shade. The dyes and prints obtained on the cotton have good wet fastness and good

  the light. In addition, they are resistant to oxidation

  tion. Preparation of starting material B

  a) 9.6 parts of 2-amino-naphthalene acid are dissolved

  3,6,8-trisulfonic acid in 60 parts of water at pH 12

  addition of 4.3 parts of a 30% solution of hydro-

  sodium hydroxide. To this solution, 11 parts of 30% hydrochloric acid are added dropwise and the suspension thus obtained is stirred well. After addition of 25 parts of ice, the diazotization is carried out at 05 by adding 6.5 parts of a 4N solution of sodium nitrite. This solution of the diazonium salt is added over a period of 30 minutes to a suspension of 3.9 parts of 3-aminophenylurea in 25 parts of water to 37 containing ice. During the addition, the pH is maintained at 5.0 by the addition of 22 parts of a 20% solution of sodium carbonate. He is

  forms a red solution containing the amino compound

azzique of formula A. S03H

N NN-M NH

H2 (A)

S03H S03H NHCONH

  B) 5.1 parts of cyanuric chloride are stirred for 30 minutes in 30 parts of water and ice. The solution obtained under a) is then added in the course of 5 minutes and the condensation is carried out at pH 6.0 in the presence of 8 parts of a 20% solution of sodium carbonate. To the orange-red solution thus obtained,

  add a solution containing 3.3 parts of 1,2-diamine

  nopropane in 50 parts of water and ice, the pH of which was adjusted to 6.0 by the addition of 8 parts of 30% hydrochloric acid. Within one hour, the temperature of the reaction mixture is slowly raised to 48-50 °. Simultaneously, the pH of the mixture is maintained at 6 by addition of 20 parts of a 20% solution of sodium carbonate. Before separating the orange compound thus formed, the precipitation of the product is completed by the addition of 100 parts of sodium chloride. The compound of formula B is thus obtained. EXAMPLES 2 TO 200 Using the procedure described in Example 1 and using the appropriate starting materials to form the desired chromophore part F 0, the non-metallized compounds of formula I collected in tables 1

to 11 following.

  The compounds of Examples 2 to 200 may be applied to substrates containing or consisting of cellulose fibers, in particular on textile materials made of cotton, by the conventional method of exhaustion dyeing or conventional printing processes. The shades obtained with these compounds are indicated in the tables. Cotton dyes and prints have good light and wet fastness and are

resistant to oxidation.

  The divalent group as defined in column "W" of heel 1 and also in each table

  later, may be an asymmetrical diamino group. normally

  In this case, the junction with a carbon atom of the triazine ring on one side and with a carbon atom of the pyrimidine ring on the other side is carried out in the order indicated. However, depending on the preparation of the starting material, this order in which the junction is made can be reversed, that is to say pyrimidine ring / triazine ring, when the starting material used is the condensation product of the derivative. of the

pyrimidine with diamine.

  TABLE I: / Compounds of Formula (Tl) R.9 W N> -Ci

COCH3 2 3

  DT N-N = N-CHCON E1NH / --- / N (Tl) Cl 1C

Ex. No. DT R1 R9. - V -

(position)

2 HO3 S - H -SO3H (3) -NHCH2CHNH-

CH3

3 do. H do. -NHCH2CHCH2NH-

- OH

  CH3COHN <CH3-SO3H (3) -NH (CH2) 3N-

- 0 HCH3

S03 So03H [

<H H -NHCH2CH2NH-

SO H

  6 <COHN -9 H -S03H (2) -NHCH2CHCH2NH-

-I OH

O C SO H

7 aC H do. do.

3 -

8 do. H do. -NHCH2CHNH-

CH3

2632651

Table I (continued)

Ex. O. DT RI. R9. - -

(position) SQ H

C3O b H -SO3H (3) -NHCH2CHNH-

CH30_ CH3

do. H do. -NH (CH2) 3N

I CH3 SO H

11 X H H -NHCH2CHNH-

I CH3 SO3H

12 do. H SO3H (3) -NHCH2CHCH2NH-

I OH

13 do. H S03H (2) -NH (CH2) 3N-

I CH3 SO3H

14H -NH (CH2) 3N-

I

SOH SO3H CH3

do. H H -NHCH2CH2NH-

16 do. H S03H (3) -NHCH2CHNH-

CH3 SO3H

17 H H do.

SO H

3 S03H

18 do. CH3 H do.

19 do. B SO3H (2) do.

  Dyes and impressions obtained on -

  cotton with the compounds of Examples 2-19 present a

greenish yellow shade.

  TABLE 2 / Compounds of Formula (T2) C1 and R2 COCH3 8

- NHR> N = N-CHCONH R9 (T2)

CN CI

R3 R4 10

  Ex. No. R2. R3. R4. R R9 R. Ro. - W -

H H -SO 3 H H H H NCH 2 CH 2 NH

  21 H H do. CH3 -SO3H CH3 -NHCH2CHNH-

CH3

22 CH3 OCH3 H do. do. OCH3 do.

23 do. CH3 H do. do. do. do.

  24H H -SO3H do. do. do. -NHCH2CHCH2NH OH

  CH3 OCH3H -SO3HH -SO3H -NH (CH2) 3N-

  CH 3 The dyes and cotton prints obtained with the compounds of Examples 20 to 25 show

a greenish yellow shade.

  eaepaA eune [C eaDuenu auin quéesead 6z e 9Z seiduexe sep sasodmoD sea DeAe senueaqo uoloo ans suoTsse2dmT salt the healthy; uTea sae úHD

-HNHDOHDHN- 8Z

HD

-HNHD0HDHN- LZ

HO

-HNHHDH0 HDHN- 9Z

- - o 'XE

0 H OS

NO IID -

  H el) alnuuo; TABLE 4 / Compounds of formula (T4) R3 OH and N = 1

D N 1N

DT4 N-- 'NI

R12 W N (T4)

  CN Cl The shade of the dyes obtained on. the cotton is indicated in the last column I or a means greenish yellow and

b means yellow.

  position Ex. No. DT4 R12 TO R13 TO - NH - - W -. I HO3S CH3H5 NHCH2CHNH- b

3

  CH3 31 do. do. H 5 -NHCH 2 CHCH 2 NH-b OH SO H 32 do. H 4 do. b 33 do. do. H 4 -NHCH 2 CH 2 NH-b 34 do. do. H 5 -NHCH 2 CHNH- b CH 3

44 2632651

  TABLE 4 (continued) position Ex. No. DT4. R12. R13. - NH -. - W -. I SO3 H

-NHCH2 CHNH-

CH3 H 4 CH3 b

SO3H SO3H

  SO 3H 36 do. H 5 do. b SH SO3H $ 033 37 CH3COHN -COOH -SO3 H5 NHCH2CHCH2NH- a OH SO3H

38 do.

  38 / do. do. 4 -NHCH2CHNH- a / - h'HCOCH3. CH3

NHCOCH

  39 HOS> do. do. 5 do.a SO3 3 do. do. 4 do. b SO, 3H 41 do. do. do. 4 NHCH2CH2NH- b

2632651

  TABLE 5 / Compounds of formula (T5) ci

N IR 14

* C1 -leg -N = / ', - 5 - N: R

X1 4 / = N R13 '1 5 (T5)

CN CN R13

R R3 R12

  R2 The shade of dyes obtained on cotton is given in the last column I o a means greenish yellow and

b means yellow.

TABLE 5

  position Ex. No. - V - -N = N-. R2. R3. Rl1. RL12. R13. R14 R15. ## STR5 ## 4 H do. OH do. C1 do. 5C1b 44 do. H 4 SO 3 H OH COOH CH 3. H a do. SO3H do. OH CH3 C1 5S03H H has 46 do. 4 H 5 -SO 3 H NH 2 H 3 -SO 3 H H 47 -NHCH 2 CHCH 2 NH-5H 4 SO 3 H do. H 4 -SO 3 H H OH 48 do. 5 h do. OH do. C1 do. H to N) Ln4 o. TABLE 5 (continued) position Ex. No. - W - -N = N-. R2. R3. Apply. R12 R13 R14 R15. ## STR5 ## ## STR2 ## 4 H do. OH COOH H 4 -SO 3 H H b 51 C SO3H 4-SO3H OH CH3 SO3H do. NUCH2CHNH-4H 5-SO3H NIt2 do. H. 3-SO 3 H H b CH 3. 53 do. 4 H H do. do. SO3H 5-SO3H H b 54 do. 4H 5 -S03H OH Cl do. H b do. 5 H 4 -SOH OH COOH CH 3 4 -SO 3 H H to 56 do. SO3H do. OH do. H do. H to 57 do. 5 h do. OH CH3 Cl. ## STR2 ## ## STR2 ## H b CH3 59 do. ## STR5 ## ## STR2 ## S03H do. ## STR5 ## OH-CH (CH 2) 4 CHNH-5H 4 -SO 3 H OH do. do. H = COOH TABLE 6 / Compounds of formula (T6) C1

CN R 14

  N.NH.Cl.sub.4 N = -T6) Cl CN 3'CN 1 R R 3

C3 'CONH 13-

R3 12

  The shade of the dyes obtained on cotton is indicated in the last column I of the table where greenish yellow means

b means yellow.

  position position Ex. No. - W -. ## STR5 ## 4 '4-SO3H OH do. do. 5-SO3H b 64 do. 3 '4 do. NH2 do. H 4 -SO 3 H -NHCH 2 CHCH 2 NH-3 '4 do. OH do. -SO 3 H 5 -SO 3 H b OH 66 do. 4 'SO 3 H OH COOH CH 3 4 -SO 3 H has 67 do. 4 '3 do. OH do. H do. ## STR5 ## b CH3 69 do. 3 '3 4-SO 3 H NH 2. Cl 5-SO 3 H a. 4 '4-SO3H OH do. -SO 3 H 4 -SO 3 H b 71 do. 4 '4 do. OH COOH CH3 do. b TABLE 7 / Compounds of formula (T7)

Q 2 N N / C;

O0 ci N (T7)

<N OH R3. R4 T

Q-4 CN Ci

Ex. No. R3 R4 Q2 Q3 Q4 - V -

  72 -SO3H H CH3 -S03H CH3 -NHCH2CHCH2NH-

OH

73 do. H do. do. do. -NHCH2CHNH-

CH3

74 do. -SO3H do. -CQNH2 do. do.

do. do. do. do. -CH2CH3 do.

  76 do. H do. -CH2SO3H do. -NHCH2CH2NH-

77 do. -SO3H do. H do. -NHCH2CHNH-

CH3

78 do. do. -COOH H H do.

79 do. H do. H H -NHCH2CHCH2NH-

OH

H 2 CH 3 SO 3 H CH 3

  81 -SO3H H do. -CONH2 do. -N NCH2CHzNH-

82 do. H CH3 H -CH2CH2SO3H -N N-

  83 do. -SO3H do. H - (CH2) 3NHC3 -NH NH-

  84 do. do. do. -CONH2 -CH2CH3 -NH (CH2) 4CHNH-

': COOH

TABLE 7 (continued)

Ex. No. R3 R4 Q2 Q3 Q4 - W -

  -SO3H -SO3H CH3 -CONH2 -CH2CH3 -HN NH-

-H N - N-

86 do. H do. -CH2SO3H H -HN - NH-

  S03H The dyes and prints obtained on cotton with the compounds of Examples-72 to 86 show a

greenish yellow shade.

  TABLE 8 / Compounds of formula (T8) Q2 c

Q X N = NC NHCO <_ <N (T8)

I OHSO3H R4 NH-

Q4

CN C1

position

Ex. No. R4 Q3 Q4 - w -

  87 H CH3 -CH2SO3HH3 -NHCH2CHCH2NH-

OH

88 H do. do. CH3 4 do.

89 H do. do. -CH2CH3 3 do.

H -COOH H H 3

91 H CH3 -SO3HH3 do.

  92 -SO3H do. -CH2SO3H H4 -NHCH2CHNH-

CH3

93 do, do. -CONH2 -CH2CH3 4 do.

94 H do. -CH2SO3H do. 3 do.

MCID

(61) N

O- OH

ID N

  b N = N- (6) anmuxo; ap ssodoD / 6 nV'ieV & eaIpaa auntC azuenu oun lu8luaesa8d 66 e úL8 Slduaxe sep sasodwoz sael Daaeooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooo its namesofdeepthedueandtheirbeauty8d 66th?

-N N- HDHD-H IHD H 66

  ## EQU1 ## HN-CH HZOSZHD-HtOSZHD-H L6 op HCOSZHDZH-H úHD HCOS-96

  -HNHD2HDHN- E HD ZHNOD- HEOS'HD- H 56

  - - -HN- Co 0 0 E 'ON' x uotzlsod (a; Lns) g nV31VIL

L S9 29 ZS

[ES9Zú9Z

  The shade of the dyes obtained on cotton is indicated in the last column I of the table where it means greenish yellow and

b means yellow.

  The carbon atom marked with an asterisk in a divalent group in column B of the table means that

  is linked to the nitrogen atom of the pyridone ring.

  In Table 9, DT9 can be a remainder

Cl -

N N

R N

R50 3

  According to the meaning of Rso and Rsl, the corresponding remains are designated DD1 to DD12, the remains DD1 to

  DD12 having the following meanings.

  So H S3 DD1 RNH - and Rso = H DD2 R5s = do. and R 50 = SO 3 H SO 3 H DD 3 R 50 = Net R 50 = H CH 3 SO 3 H DD 4 R 5 = NH and R 50 = H

Rsl Q- -

  S0-3H S03H DD5 Rs1 and R50 = SO3H DD6 R5B, H03S- "NH - and R50 = H

- 2632651

  SO H 803H NH-DDI Rs = X and R5soO = H so1 {

3 S03H

DDS R51 = do. and Rso = SO3H

HO SNIH-

DD9 R51 = and R5 o = H O H

S03H S3H

SO03H S03H

  S03H DD11 R51 = X.H t.R O NH- DD1I R51 = and R55 = HS Ds and Rso B.

SO3H S03H

  Moreover, DTg can mean a remainder

C1 N N R NH- CONIH t

R0 5031

R50 3SO3H

  in the corresponding groups which are designated DD13 to DD21, o Rso and R51 have the following meanings: SO H DD13 R5 = NH-_- and Rs0 = H DD14 R51 H03s- (-NE and Rs0 SO3H

= H03SSa--

  DD1 s1 = / N and Rso = H CH3 SO 3H DDI6 Rs = and Rso H SO3H S03HHH DDI7 R5 e = R. = H -NH DD1 to R5X = N \ 3 NH and R50 = H

SO H SO3H

SH S03 H

03 3

SQ H NH- DDI9 R51 = and R0 S03H

- CH3 S

DD2 o Rs51 =. \ H = N - and R0 H

CH S

S03H DD21 Rs, t Rl 3 $ 3

TABLE 9

Ex. No. DT9 Q2 Q3 - B - - W -

  CH3 -CONH2- * CH2CH2NH- -NHCH2CHCH2NH- a H ouz

SO H S3H.OH

  101 do. CH 2 CHNH -NHCH 2 CH 2 NH-CH 3 102 HO 3 S do. -CH2SO3H - '(CH2) 3N-NHCH2CHNH- a

CH3 CH3

"S03H

  104 do. -CH2SO3H -CCHC2NH-NHCH2CHCHNH- b CH3 SO H

SO3H -

  104 do. -CONH2SH - (CH2) 3CH2NH - NHCH2CHCH2NH- a

503H S0 H. CE3 CH3

SO H 1 3.

-CH 2 SO 3 H -CNCHNHCl. b-

3 3: HO S

7do. -CONH - * (cCH) NH- -NHCH2CHNH-

SOH CH3 CH3

S 0 H S

3 0 3

  ## STR2 ## b So CH3 $ 3H 107 CH3 H - CH2 CH2N'H-NHCH2 CH2 NH- b

S03H SO3H

  TABLE 9 (continued) Ex. No. DT9 Q2 Q3 -B- -W-I S03H 108 -CH2SO3H-CH2SO3H- * CH2CH2NH- -N NCH2CH2NH- b% / / 3H 03H 109 HO3 CH3 -CONH2 - * CH2CHNH- -NH \ -NH- a

O3S - -

  CH3 SO3H do. ## STR5 ##

CH3 OH

  SO3H CH3 112 H03 S do. do. -'CH2CHNH- -NH (CH2) 3N- b

CH3 CH3

  SO 3 H SO 3 H 113 CH 2 SO 3 H -CONH 2 - (CH 2) 3 N -doc. ## STR5 ## -NHCH2CH2NH- a

NCOCH3

NQHCOCH3 TABLE 9 (continued)

Ex. No. DT9 Q2 Q3 B- - -

  H3S 3 CH3. -CH2SO3H -'CH2CHNH- -NH (CH2) 3N- a f

NHCO. - '' - '' - 'CH3 CH3

  SO H 3. 116 H3S 9 do. do. - '(CH2) 3N- -NHCH2CHNH- a

I I

NHCO CH3 CH3

  117 DD1 CH3 H -CH2CH2NH- -NHCH2CH2NH- a 118 do. do. -CONH2 -CH2CHNH- do. at CH3 119 do. do. H do. -NHCH2CHNH- CH3 DD2 do. -CONH2 do. -NH (CH2) 3N- CH3 121 do. do. -CH2SO3H-CH2CH2NH- do. a 122 DD3 do..SO3H -'CH2CHNH-NHCH2CHCH2NH- a

I. I

  tCH3 OH 123 DD4 do. H do. -NHCH2CHNH- a

- CH3

  124 do. do. -CONH 2 - '(CH 2) 3 NSO-. a DD5 do. -CH 2 SO 3 H - '(CH 2) 3) N-do. CH3 126 DD6 do. -CONH2 -CH2CH2NH- do. at 127 do. do. H do. -NH (CH2) 3N- CH3 128. DD7 do. H do. -NHCH2CHNH- CH3 129 DD8 do. -CONH2 - * CH2CHNH- do. a CH3 do. do. H do. ## STR3 ## H do. do. at 133 DDI1-CH2SO3H-CH2SO3H do. do. a 134 DD12 do. -CONH2 * (CH2) 3N- -NH (CH2) 3N- a

CH3 CH3

  DDL3 CH3 do. do. do. at 136 do. do. H-CH2CH2NH- - do. a 137 DD14 do. CH2SO3H do. -NHCH2CHNH- a13 CH3 138 DD15 do. H do. do. at 139 DD16 do. CONH2 - * CH2CHNH- do. a CH3 do. do. H'CH2CH2NH- do. at 141 DD17 do. CH2SO3H - '(CH2) 3N- -NH (CH2) 3N- a

CH3 CH3

  142 DDz8 do. H do. -NHCH2CHNH- CH3 143 DD19 do. -CH2SO3H - * CH2CH2NH- do. a 144 DD20 do. -CONH2 do. do. a do. do. HCH2CHNH- do. CH3 146 DD21 do. -CONH2 do. TABLE 10 Compounds of Formula (T10) S03H NmN / NH / N) X2 R) = / N f Ci1 (T1O) 503H (SO3H) CNCl The shade of the dyes obtained on the cotok is indicated

  in the last column I of table o.

  b means yellow c means yellowish orange and

d means orange.

  Ex. No. position m R6 R-W-I-N = N- (position) 147 2 1 (3) H -NHCONH2 NHCH2CHCH2NR- d OH 148 2 1 (4) H do. do. d 149 1 1 (3) H do. do. d - 2 O H CH3 do. b 151 2 1 (4) H do. do. b 152 1 1 (3) H do. do. b 153 2 1 (3) H H do. b 154 2 0 H; H do. b 2 1 (3) CH3 CH3 do. b 156 2 1 (4) OCH3 H do. b 157 2 1 (3) H -NHCOCH3 do. c 158 1 1 (3) H do. do. c 159 1 1 (3) H NHCONH2 -NHCH2CHNH- d CH3 TABLE 10 (continued)

Ex. No. position m R6 R7 - -

  -N = N- (position) H -NHCONH2 -NHCH2CHNH-d CH3

161 2 1 (4) H do. do.

  d 162 2 1 (3) H H do. b b 163 2 1 (3) H -NHCOCH3 -NHCH2CHNH- c CH3 164 1 1 (3) H do. do. c 2 O H do. do. c 166 2 1 (3) H CH3 do. b 167 2 1 (3) OCH3 H do. b 168 2 1 (3) H -NHCONH2 -NHCH2CH2NH- d 169 2 1 (4) H do. do. d 1 1 (3) H do. do. d 171 2 1 (3) H CH3 do. b 172 2 1 (3) H H do. b 173 2 1 (3) H -NHCONH 2 -N N -d 174 2 1 (4) H CH 3 do. b 2 1 (3) H -NHCONH 2 -N-CH 2 CH 2 NH-d TABLE 11 / Compounds of formula (T11) n SO N N = N = ci (T11) R7

S O3H

(SO3H) m CN CI

TABLE 11

m

Ex. No. (position) R7 - W -

176 1 (4) CH3 -NHCHzCHNH-

CH3

177 1 (4) -CH2CH3 do.

178 0 CH3 do.

179 1 (3) do. do.

1 (4) do. -NHCHZCHCH2NH-

OH

181 1 (4) -CH2CH3 do.

182 0 do. do.

183 0 CH3 do.

184 1 (3) -CH2CH3 do.

1 (4) CH3 -NHCH2CH2NH-

186 1 (3) do. do.

187 0 do. do.

188 1 (4) do. -NH (CH2Y3N-

CH3

189 1 (4) do. -N N-

1 (3) -CH2CH3 do.

191 0 CH3 -N NCH2CH2NE-

192 1 (3) H -NH (CH2) 3N-

CH3

193 1 (4) H do.

TABLE 11 (cont'd) m

Ex. No. (position) R7 - W -

194 1 (3) -NHCOCH3 -NH (CH2) 3NH-

1 (3) do. -NHCH2CHNH-

CH3

196 1 (3) -NHCONH2 do.

197 1 (4) do. do.

198 1 (3) H do.

199 1 (3) -NHCONH2 -NH (CH2) 3N-

CH3

1 (3) do. -NH (CH2) 3NH-

  The dyes and prints obtained on the cotton with the compounds of Examples 176 to 200 show a

orange shade.

EXAMPLE 201

  15.6 parts (0.02 moles) of the Cu SO3H compound are dissolved.

3 SOH

I 3

N = N N = N

S03H CH3 H2

  S03H in 300 parts of water at pH 8.5-9. The pH is set to 6.0

  by adding a small amount of hydrochloric acid.

  To this solution, 3.9 parts (0.02 mole plus%) of cyanuric chloride are added and the pH is maintained at 5-6.5 by addition, with stirring to 10-15, of a solution of dichloromethane. 'sodium hydroxide. After about 1 hour, the

reaction is over.

  To the resulting reaction mixture (0.02 mol),

  1.6 parts (0.02 mole plus 10%) of 1,2-diamino-

  propane. Condensation is carried out at 40-50 and the pH

  is maintained at 5.5-6.5 by addition of a solution -

  of sodium hydroxide. The reaction is complete after

about 2 hours.

  To the fine suspension thus obtained (0.02 mol),

  4.6 parts (0.02 mole plus 10%) of 5-cyano-

  2,4,6-trichloropyrimidine. The reaction is carried out at -20 and at pH 8.5-9.0. After salting out, filtration and drying, the compound of formula Cu.sub.2 H.sub.2 O.sub.2 is obtained.

3 0 SO3H

N = NN

ÀN '

-N Cl S03H CH3 -m

S03H N N

3 '3 -3C

50311. NECH CHINH

  CN Ci dyes cotton in a blue shade. The dyes obtained on the cotton have high fastness to light and good wet fastness and are

resistant to oxidation.

EXAMPLES 202 to 291

  By proceeding as described in Example 201 and using the appropriate starting materials to form the desired chromophore moiety Fc, metalliferous complex compounds of Formula I are obtained which are collected in

Tables 12 to 17.

  The metalliferous complexes of Examples 202 to 291 dye the substrates containing or consisting of cellulose fibers, in particular cotton textile articles, in the indicated shade, the dyeing being carried out according to the conventional method by

  exhaustion and printing according to conventional methods.

  The dyes and prints thus obtained on cotton have high fastness to light and

  wet and are resistant to oxidation.

  TABLE 12 / Compounds of Formula (T12) Cu 0 /, O0 So H S3H T12 N (T12) N R52 Sa - - C

2 S03H N = C 1

CN C

Ex. No. DT12 R52 -

S03 H

202 CH3 -NHCH2CH2NH-

* S03H

203 do. do. -NH (CH2) 3N

CH3 - TABLE 12 (continued)

Ex. No. DT12 R52 - W -

______________________52

SO 3

204 'CH3 -NHCH2CCH2NH-

OH

205 E H -NECH2CN-

CH3

206 H03S H do.

S03H

207 cO CH3 -NH (CH2) 3N-

CH3 Sa H

208 H3C do. do.

H3

- SO H

209 do. H -NHCH2CHNH-

CH3

211- da. CH3 -NHCH2CH2NH-

-SO3H

212 0e do. -NH (CH2H) N-

EH3 03HCH ID ND

9 ID N N9

0 = N \ / N = N

  <;, r) elnuinog ep sesoduioo / EJ nYi 'N & -aneIq has been used to us uoIoD and queubTeq VIZ Q Z0Z seIdumaxe sep sesoduio0 ser op H 17IZ

H OS / HOS

H HS OS ú

HOHS S

-HNZHDH3OHDHN- RD

  -M- E% 0NLia 'oN' x3 (a; Lns) Z [flV3q V / L s9 229 z

TABLE 13

  position Ex. No. R2 R29 Rs2 -NH- -W- q (position)

215 H H H 4 -NHCH 2 CH 2 NH-2 (3.6).

  2-0CH3 3-SO3H-CH3 5 -NHCH2CHNH-2 (3,8)

CH3 217H do. H 5 do. 3 (3,6,8)

  218 2-OCH3H CH3 4 - -NH (CH2) 3N- do.

CH 3 219 2-CH 3 H H 5. 2 (4,6)

  220 H 2 -SO 3 H 4 NH (CH 2) 3 NH-2 (3.8)

221 H do. H 4 -NHCH 2 CHNH-do.

  CH3 222H do. CH3 5 do. 2 (3,6) 223 H do. H 4 do. 3 (3,6,8)

224 2-OCH3 3-SO3HH5d. do.

225 do. do. H 5 -NH (CH 2) 3N- do.

CH3

226 do. do. H 5 -NHCH 2 CH 2 NH-do.

  The compounds of Examples 215 to 226 dye cotton in

a blue shade.

  TABLE 14 / Compounds of formula (T14) Cu - C

R NN - N

SSO Hh (T14)

3. CI

CN Cl

263265 1

TABLE 14 (continued) position

Ex. No. SO3H R17 R1 - W -

227 4H H -NHCH2CHNH-

CH3

228 4 H CH3 do.

229 6 H H do.

230 4 6 -Cl H do.

231 4 do. CH3 do.

232 6 4-Cl H do.

233 4 6 -COOH H do.

234 4 6-SO3H H do.

235 4 do. CH3 do.

236 4 H H -NHCH2CHCH2NH-

OH

237 6 H H do.

238 6 4-CH3 H do.

239 4 6 -Cl H do.

240 4 6-SO3H H do.

241 4 do. H -NHCH2CH2NH-

242 4 H H do.

243 4 6-NO2 H do.

244 4 6 -Cl H do.

245 6 4-Cl H do.

246 4HH -NH (CH2) 3NH-

247 4 6 -Cl H do.

248 4 6-SO3H H do.

249 4 do. H -NH (CH2) 3N-

CH3

250 4 do. H -N N-

  The compounds of Examples 227 to 250 dye cotton in

a ruby red shade.

  TABLE 15 / Compounds of formula (T5s) Cu - /

NE </ \

SO H HO3S 3 Cl

Ex. No. - U. -

CISOR (T15)

N - K 3

N cxci

Ex. No .--

251 -NHCH2C) 2NH-

252 -NHCH2CHCH2NH-

OH

253 -NH (CH2) 3NH-

254 -NHCH2CHNH-

CH3

255 -NH (CH2) 3N-

CH3

256 -N N-

  The compounds of Examples 251 to 256 dye cotton in

a dark blue shade.

  TABLE 16 / Compounds of Formula (T16) Cu

2 8

R I .. t -N-SH) r 4 c 6 C 1 (S 3 H 6)

N-KSO3H 5

  NIH i N htN ci CN C1 The shade of the dyes obtained on cotton is indicated in the last column I of the table, where g means ruby and

h means purple.

TABLE 16

position-

  Ex. No. Rs50 -NH-r (position) 257 5-SO3H 3 -NHCH2CH2NH- 1 (6) g 258 do. 3 -NHCH2CHNH- do. CH 3 259 3-SO 3 H 5 do. do. g 260 do. NHCH2CHCH2NH- do. OH 261 5-SO3H 3 do. do. g 262 do. 3-NH (CH 2) 3 N -doc. g CH3 263 H4 do. 2 (6.8) h 264 H 4 -NHCH 2 CHNH-d 2. h CHE3 265 H 5 do. do. h 266 H 4 -NHCH 2 CH 2 NH-do. h 267 H 4 -NH (CH 2) 3 NH-d. h 268 H 4 NCH 2 CHC 2 NH-c. h

-IC2 C2NH-

  TABLE 17 (Compounds of Formula (T17) C-3f NH- (/ N

4. X ^ 2 w 4 N-

  3) p 5t. 1- (1C)> 5I I (S03H) m - N> CN Cl (T17)

C.1011 (T17)

6 2

3

R R.

R20 R21

TABLE 17

p position m

  Ex. No. (position) XI X2 -NH- (position) R20 R21 - -

  269 2 (3 ', 5') -O- -COOH 4 O 2 -SO 3 H -NHCH 2 CH 2 NH-

  270 do. do. do. 4 O do. H -NHCH2CHCH2NH-

OH

  271 do. do. do. 4 O do. H -NHCH2CHNH-

CH3

272 do. do. do. 4 0 3-SO3H H do.

  273 do. do. do. 4 O do. H -NH (CH2), N-

CH3

  274 1 (4 ') -COOH-O-1 (5) H -NHCH2CH2NH-

  275 do. do. do. 3 do. HH -NH (CH2) 3NH-

  276 do. do. do. 3 do. H H -NHCH2CHCH2NH-

OH 277 do. do. do. 3 do. HH -NHCH2CHNH-

CH3

278 do. do. do. 3 do. 3-SO3H H do.

  279 1 (5 ') do. do. 3 do. 2-C1H do. ro 280 do. do. do. 3 do. 2-C1 5-C1 do. tw 281 do. do. do. 3 do. 2-SO3H H do. o, Table 17 (continued) position P

  Ex. No. (position) XI X2 -NH- (position) R20 R21 - V -

  282 1 (5 ') -COOH -O0- 3 1 (5) 3-SO3HH -NHCH2CHCH2NH-

011. '

283 do. do. do. 3 do. 4-SO3H H do.

  284 do. do. do. 3 do. 4-CH3H -NHCH2CH2NH-

285 do. do. do. 3 do. 4-OCH3H do.

  286 do. do. do. 3 do. 3-CH3 4-Cl -NH (CH2) 3N-

CH3

  287 1 (4 ') -O-COOH-1 (5) 2-CH3 H -NHCH2CHNH-

CH3

288 1 (5 ') do. do. 5 1 (3) H H do.

  289 do. do. do. 5 do. 2-CH3H -NHCH2CHCH2NH-

OH

  290 do. do. do. 5 do. 4-SO3HH -NHCH2CH2NH-

291 do. do. do. 3 1 (5) H H do.

  The compounds of Examples 269 to 291 dye cotton in

a blue shade.

EXAMPLE 292

  45.3 parts of the monoazo compound of formula SO HO are dissolved

S3H OH

CH3 0 N = N

3 -

  prepared according to the known methods, in 700 parts of water and is added at 20-25o, in the space of 30 minutes, 18.5 parts of solid cyanuric chloride. The mixture is stirred at pH 6.0-6.5 until no free amino group can be detected. 11.1 parts of 1,2-diaminopropane are then added and the reaction mixture is stirred for two hours, the pH being maintained at 7.0 by the addition of a dilute solution of sodium carbonate. The condensate is salted out by the addition of sodium chloride and filtered off. The wet paste thus obtained is dissolved in 900 parts of water. To this solution was added 24.9 parts of -cyano-2,4,6-trichloropyrimidine and stirred for two hours at 0-5. During the reaction, the pH is maintained at 8-9 by addition of a dilute solution of sodium carbonate. The compound obtained is precipitated by adding sodium chloride and isolated. It corresponds to the formula sa H OH CH O N =% * ci

3 -N- -

S 03H C 1

SHCH CHN1 -2

  In the dry state, the compound is in the form of a dark red powder which dissolves in water giving a red solution. It dyes the cotton in a scarlet shade. The dyes obtained have good fastness to light and wet and are resistant to oxidation. Examples 293 to 319 - By proceeding in a manner analogous to that described in Example 292 and using suitable starting materials, other compounds of formula I can be prepared. They correspond to formula (T18)

SO3H OH

R N Ci

3 - <

S O H NH ô / N

  Wherein the symbols are as defined in Table 18, hereinafter. The dyes obtained with the compounds of Examples 293 to 319 have good

  light and wet fastness and are resistant to

oxidation.

  In the last column I, the shade of each

  cotton is indicated as follows d means orange and k means scarlet Table 18 /-- compounds of formula 1 (Tl8) Ex. No. R3 R4 - W - I 293 OC2H5s H -NHCH2CHNH- k I CH3 294 OCH3 SO3H do . k 295-C 2 H 4 OH H do. k 296 OCH3H -NHCH2CHCH2NH- k OH 297 do. SO3H do. k 298.-0C2H40 OH H do. ## STR5 ## wherein OCH 3 SO 3 H -NHCH 2 CH 2 NH-k 301-OC 2 H 5. k 302 -OC2H40OH H do. ## STR2 ## S03H do. k 305 OC2H40H H do. k 306 0C2H5H -NH (CH2) 3N- k! CH3 307 OCH3H -NN- k 308 do. SO3H do. k 309 -OC2H40H H do. k 310 -OC2H40C2H40H H do. k 311 do. H NHCH2CH2NH- k 312 do. H -NH (CB 2) 3 NH-k 313 do. ## STR5 ## d 316 do. do. -NHCH2CHCH2NH- d OH 317 do. do. NHCH2CH2NH- d 318 do. do. -NH (CH2) 3N- CH3 319 do. H do. d

Example 320

  In a mixture of 10 parts of water and 20 parts of ice, the mixture is stirred until a

  homogeneous suspension 5 parts of cyanuric chloride.

  To this suspension is added a neutral solution (pH 7) of 30 parts of tetrasodium salt of the compound of the formula

SO H OH NH

3 * 2

* a N - N

N N -N =.

S O HH SO H

  in 160 parts of water and the mixture is stirred at 50 and at pH 5.5-6.0 until no amino group can be detected. At pH 6.5-7.0, the

  temperature at 15 and 3.25 parts of 1,2-di-

  aminopropane. The pH is maintained at 6.0 by the addition of hydrochloric acid. The mixture is heated at 50 for 3 hours to complete the reaction. 70 parts of sodium chloride are then added and

  filter the red suspension. The filter cake is washed

  with 500 parts of a 20% sodium chloride solution. The resulting paste is poured into 500

  parts of water and add 4.5 parts of 5-cyano-

  2,4,6-trichloropyrimidine. The mixture is stirred

  12 hours until the reaction is complete.

  and 80 parts of sodium chloride are added. The compound thus obtained is precipitated and filtered; it corresponds to the formula SO H C1 $ 03H - H0 HN-X-ff es N.HCH CIHNHNC

S03 H S03 H 3 -

  In the dry state, the compound is in the form of a dark red powder which dissolves in water, giving a red color. It dyes the cotton in a bluish red shade. The dyes on

  cotton have good general fastness.

Examples 321 to 416.

  By proceeding analogously to that described in Example 320 and using the appropriate starting materials, other compounds of formula I which are indicated in Tables 19 to 22 below can be prepared. Cellulosic fibers and in particular cotton can be dyed with the compounds of Examples 321 to 416 by the usual method of dyeing by exhaustion. All dyes are bluish red and have good fastness. Table 19 / Compounds of formula (Ti9) Cl

8 1 HO NH

-... 2 N__. - c ..

W =: 1 (T19)

(S) 3H SO-H SO3H S0 3

3 r CN Cl.

Ex. No. m position of the - w -

groups S03H

321 0 1 -NHCH2CHNH-

CH3

322 0 1 -NHCH2CHCH2NH-

OH

323 1 1.5 do.-

324 1 3.6 do.

325 0 1 -N N-

326 1 1.5 do.

327 0 1 -NHCH2CH2NH-

328 1 1.5 do.

329 1 4.8 do.

330 O 1 -NH (CH 2) 3 NH-

331 1 1.5 do.

332 0 1 -NH (CH2) 3N-

CH3

333 1 1.5 do.

334 1- 3.6 do.

335 1 4.8 do.

336 0 1 - -NHCH2CH2N-

CH2CH2OH

337 1 4.8 -NHCH2CHNH-

CH3

84> 2632651

  Table 20 / Compounds of formula (T20) C1

(SO3H)) -N-

  R f N = N N =; ci (T20) 324 mN3 03H> - N

CN C1

  Ex. No. m (position of R3 group S03H)

338 1 (2) H H -N N-

339 do. 5-SO3H H do.

340 do. do. 4-CH3 do.

341 do. do. 4-OCH3 do.

342 do. H 4 -CH 3 do.

343 do. H 4-0CH3 do.

344 do. 4-SO3H H do.

345 do. H H -NHCH2CH2N-

I

CH2CH2OH

346 do. H 4 -OCH 3 do.

347 do. 5-SO3H H do.

* 348 do.H 4 -CH3 -NH (CH2) 3N-

I CH3

349 do. H 4 -OCH 3 do.

350 do. H H do.

351 do. 5-SO3H H do.

352 do. 4-SO3H H do.

## STR2 ##

354 0 3-COOH H do.

355 0 4-COOH H do.

  356 1 (2) 5-S03H 4-OCH3 -NHCH2CHCH2NH-

OH

357 do. H H do.

358 do. H 4 -CH 3 do.

-2632651

Table 20 (continued)

Ex. No. m (position of R3 R4 - -

group S03H)

359 1 (2) H 4 -OCH3 -NHCH2CHCH2NH-

OH

360 do. 4-SO3H H do.

361 0 3-COOH H do.

362 1 (2) H H -NHCH2CHNH

CH3

363 do. 5-SO3H H do.

364 do. do. 4-CH3 do.

365 do. 4-SO3H H do.

366 0 2 -COOH H do.

367 0 3-COOH H do.

368 0 4-COOH H do.

369 1 (2) HH -NHCH2CH2NH-

370 do. H 4 -OCH 3 do.

371 O 2 -COOH H do.

372 1 (2) 5-S03HH -NH (CH2) 3NH-

  Table 21 / Compounds of Formula (T21) Ci

C1CN SO3H SO3H

C1 CN 3 3

  Ex. No. RI6 373 -NHCH2CH2NH-methyl 374 do. ethyl 375 do. phenyl Table 21 (continued) Ex. No. V-R16 376 -NHCH2CHNH-phenyl CH3 377 do. methyl 378 do. Ethyl 379 -NH (CH 2) 3 N -methyl CH 3 380 do. phenyl

381 -NHCH2CHCH2NH- do.

  OH 382 do. ethyl 383 -N N-methyl 384 -NH (CH2) 3NH-phenyl Table 22 / Compounds of formula (T22) 3o W CN C i

SO 3H SO H

CN ci

870 2632651

Table 22

position position

Ex.-No. S03H DT22 of -NH- -W-

SOH J

385 3 3 -NHCH2CH2NH-

NOT}

386 do. 3 4 do.

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

CH3

388 do. 3 3 -N N-

\ -J

389 do. 3 3 -NHCH2CHCH2NH-

OH

390 do. 3 3 -NHCH2CHNH-

CH3

391 do. 4 3 do.

392 3 4 do.

S3 SO3H

393 do. 4 3 do.

394 do. 3 3 do.

SORH

395 X 3 4 do.

SO H.

396 do..3 3 do.

397 do. 4 4 do.

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

  CH3 CH3 Table 22 (position position position

Ex. No. DT22 of S03H from -NH- -W-

S03H

399 / \ 3 4 -NH (CH2) 3N-

CH3 SQ3 H SO3H

400 do. 3 3 -NHCH2CH2NH-

401 do. 3 3 -NHCH2CHNH-

CH3

402 do. 3 4 -NHCH2CHCH2NH-

OH SO H

403 CH3 3 3 -NHCH2CHCH2NH-

OH

404 do. 3 4 -NHCH2CHNH-

CH3

405 do. 4 4 do.

SQ H S03H

406 H3C 3 4. do.

S03H

407 do. 3 3 -NHCH2CH2NH-

SQ H S03H

408 HO3S 3 3 do.

409 do. 4 3 do.

410 do. 3 4 -NHCH2CHNH-

I CH3

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

CH3

412 HOOC 3 4 do.

Table 22 (continued) -

position position

Ex. No. DT22 of S03H from -NH- -

COOH

413 3 4 -NHCH2CHNH-

d- - CH3 SQ H

414 3 3 do.

415 do. 4 4 -NH (CH2) 3NH-

416 do. 3 4 -NHCE2CHCH2NH-

OH

Example 417

  For 45 minutes, 212 parts of cyanuric chloride are stirred in a mixture of 560 parts of ice and 200 parts of water. We add a solution

  comprising 190 parts of 2,4-diaminobenzene-1-acid

  sulfonic acid in 920 parts of water and 112 parts of 30% sodium hydroxide solution and this mixture is stirred for 6 hours while cooling with

  an ice bath. The white suspension is later-

indirectly diazotized.

  Meanwhile, 140 parts are diazotized

  of 4-aminobenzoic acid by proceeding according to

  known thodes and under acidic conditions they are

  copula with 320 parts of 1-amino-8-hydroxy-acid

  Naphthalene-3,6-disulfonic acid. To the red suspension obtained, the above solution of the diazo is added.

  and an alkaline copulation is carried out.

  To the blue solution obtained, 120

  1,2-diaminopropane parts. Condensation is

  for 2 hours. The reaction mixture was then quenched with sodium chloride (25% of volume) and filtered. The filter cake is redissolved

  blue in water using ten times the amount.

  To this aqueous solution is added, within 2 hours, a suspension of 175 parts of -cyano-2,4,6-trichloropyrimidine in 350 parts of water and 150 parts of ice which has been stirred for minutes. The pH of the mixture is then maintained

  reaction at 9 for 3 hours. We are relegating the

  thus obtained by addition of sodium chloride (10% of volume), filtered and the filter cake was dried under vacuum. The compound obtained corresponds to the formula Ci

H2N OH

-OOC- (PEN = 5 NH NC

SO H SO H 3 CH 2 <H

3.3 CH3 -_

  CN Cl and dyes cellulosic fibers and especially cotton in a marine shade. These dyes have good solidities such as light fastness and

  wet, and are resistant to oxidation.

  Examples 418 to 456 Proceeding as described in Example 417 and using appropriate starting materials, other compounds of formula I can be prepared. They correspond to the formula (T23) R sOH SOH (T23)

4 3 3 O-

  s% W-; c CN C1 in which the symbols are as defined in Table 23 below. The compounds of Examples 418 to 456 dye the cellulosic fibers and in particular the cotton in a marine grade, by the usual dye-out method. These

  dyes have remarkable general solidities

ral.

92 2632651

  Table 23 / Compounds of formula (T23)

Ex. No. R3 R4 position R5 - W -

from -NH-

418 4-SO3H H 5 SO3H -NH NH-

SO.sub.3H

419 3-COOH H 4 do ,. do.

420 4-COOH H 4 COOH do.

421 do. H 4 SO3H -NHCH2CHNH-

I CH3

422 3-SO3H H 5 do. do.

423 5-COOH 2-Cl 4 do. do.

424 do. do. 5 do. do.

425 do. do. 4 COOR do.

426 3-COOH H 5 SO3H do.

427 4-SO3H H 4 COOH do.

428 2-SO3H 4-Cl 4 do. do.

429 4-SO3H H 4 SO3H do.

430 2-SO3H 4-Cl 4 do. do.

431 4-SO3H H 5 do. do.

432 2-SO3H 4-Cl 5 do. do.

  433 5-COOH 2-Cl 5 do. -NHCH2CHCH2NH-

OH

434 4-COOHR H 5 do. do.

435 4-SO3H H 5 do. do.

436 3-COOH H 5 do. do.

437 3-COOH H 4 do. do.

438 3-SO3H H 4 do. do.

439 do. H 4 COOH do.

440 do. H 5 SO3H -NHCH2CH2NH-

441 5-COOH 2-Cl 5 do. do.

442 5-SO3H do. 5 do. do.

443 3-COOH H 5 do. do.

444 2-SO3H 4-Cl 5 do. -NH (CH2) 3NH-

Table 23 (continued)

Ex. No. R3 R4 position Rs - W -

from -NH-

445 5-SO3H 2-C1 4 SO3H -NH (CH2) 3NH-

446 4-COOH H 4 COOH -NH (CH 2) 3N-

CH3

447 5-S03H 2-C1I 5 S03EH do.

448 4-COOH H 5 do. do.

449 5-COOH 2-C1 5 do. do.

450 3-COOH H 4 COOH -N N-

451 3-SO3HH 4d. do.

452 do. H 5 S03H do.

453 5-COOH 2-C1 4 COOH do.

454 4-COOH H 5 SO 3 H -NH (CH 2) 4 CHNH-

I COOH

455. 5-SO3H 2-C1 4 COOH do.

456 2-SO3H 4-C1I 4 do. do.

Example 457

  - In 1200 parts of water, 65.9 parts of the compound of formula

HO S C1

3S

-J N 0 NHO (CH2) 3N-H2

H2N (CH2) 3HN O "N

  SO3H prepared according to known methods. At 20-25, 37 parts of solid cyanuric chloride are added over 30 minutes. The mixture is stirred for 1 hour at pH 6.0-6.5, the pH being maintained at this value by continuous addition of a dilute solution of sodium carbonate. 22.2 parts of 1,2-diaminopropane are added and the mixture is stirred at 40-50 for 2 hours while maintaining the pH at 7 by addition of a dilute solution of sodium carbonate. The condensation product is salted with sodium chloride and filtered. The resulting paste is redissolved in 1400 parts of water. To this solution, 49.5 parts of 5-cyano-2,4,6-trichloropyrimidine are added and the mixture is stirred for 2 hours at 5-10. During the reaction, the pH is maintained at 8-9 by the addition of a dilute solution of sodium carbonate. The resulting compound is precipitated by the addition of sodium chloride and isolated. It answers to the formula N 'N oc

S03H |

N NCN C1

  In the dry state, the compound is in the form of a black powder which dissolves in water giving an intense blue color. He dyes the cotton in an intense blue shade. These dyes are very

  good solidity in the tumère and the wet.

  Examples 458 to 472 Using the procedure described in Example 457, it is possible to prepare other compounds of formula I. They are present in the following formula: ## STR2 ##

-CH CN

C3

CN CN

  In the dry state, the compound is in the form of a black powder which dissolves in water giving an intense blue color. It dyes the cotton in an intense blue nuance. These dyes are very

  good fastness to light and wet.

  Examples 458 to 472 Using the procedure described in Example 457, other compounds of formula I can be prepared. They correspond to the formula (T24) R1 Cl (SO3H) m

_ A 0_C

O0 N c

(S 0 H) C 1 -N - (CH

(S3Hm. (SQ503H) m CR1_ (T24)

CN C1

  wherein the symbols are as defined in Table 24 below. The compounds of Examples 458 to 472 dye the cotton in an intense blue shade. These dyes have good fastness to light

and wet.

  Table 24 / Compounds of formula (T24)

Ex. No. m R1 - -

458 1H -NHCH2CH2NH-

459 1H -NH (CH2) 3NH-

460 1H -NH (CH2) 3N-

I CH3

461 1 H -NHCH2CHCH2NH-

OH

462 1 H -N N-

463 0 -SO 2 CH 2 CH 2 O 3 SO 3.

464 0 do. -NHCH2CH2NH-

465 0 do. -NH (CH2) 3NH-

466 0 do. -NHCH2CHCH2NH-

OH

467 0 do. -NHCH2CHNH-

CH3

468 1 do. do.

469 1 do. -NHCH2CHCH2NH-

OH

470 1 do. -NHCH2CH2NH-

471 1 do. -NH (CH2) 3NH-

472 / do.-N N-

472 I do. -N N-

Example 473

  In 200 parts of water and at pH 6.5-7.0 25.7 parts (0.025 moles) of the compound obtained by known methods are dissolved by sulfochlorination of copper phthalocyanine and then reaction with 1,3-diaminobenzene acid. 4-sulfonic, and containing per molecule on average about 2.5 sulfo groups and 1 sufonamido group. After addition of 150 parts of ice, at 0-5, 4.6 parts of cyanuric chloride are added and the mixture is stirred for 2 hours at pH.

  6.0-6.5. 2.8 parts of 1,2-diamino-

  propane and, after stirring for 1 hour at 0-5, the temperature is raised to 30-35 within 2 hours

  and the pH is adjusted to 7.5-8.0 by the addition of a solution.

  20% sodium carbonate. The reaction product is then salted off with 70 parts of sodium chloride, filtered and redissolved in 250 parts of water. At 0-5, 6.3 parts of -cyano-2,4,6-trichloropyrimidine are added and the mixture is stirred.

  at this temperature for 3 hours. Simultaneous-

  the pH is maintained at 8-8.5 by addition of carbons.

  sodium nate. When the condensation is complete, the mixture is salted with 45 parts of sodium chloride. The precipitate is filtered off and dried at 35 ° C. The compound thus obtained corresponds to the formula X SO 3 Na) 2, 5 CuPc SON NIHH - Na

SQ NH'3 (NH- <CH

- CH

* 2 N CN C2

  N Cl C c and dyes the cellulosic fibers and in particular the cotton in a bright turquoise shade. These dyes

  have good lightfastness and excel-

 2632651

slow wet fastness.

Example 474

  By proceeding as described in Example 473 and using an equivalent amount of nickel phthalocyanine, that is 25.5 parts (0.025 mole) instead of 25.7 parts of copper phthalocyanine, we obtain the corresponding compound [NiPc] having a formula similar to that of Example 473, which dyes the

  cotton in a bluish green shade. Pre-existing dyes

feel good solidity.

  Examples 475 to 480 Proceeding as described in Examples 473

  and 474, further phthalocyanines can be prepared.

  They correspond to the formula (T25) S 03H) c MePc S 02NH2) d 2 3 R ci _, s02 l__ S s IM -IC C4, -, <(T25) W BNt

CN C1-

  wherein the symbols are as defined in Table 25 below. In the last column I, the shade of each dye on cotton is indicated as follows: e means bright turquoise and

f means bluish green.

  These dyes have good fastness.

  Table 25 / Compounds of formula (T25) position of

Ex. No. Me c d R -NE- - W -

475 Cu 3 O H 3 -NHGH 2 CHNH- e I CEH3

476 Cu 2 1H 3 do. -

477 Cu i 2 4-SO 3 H 3 do. e

478 Cu 2 1 2-COOH H do.

  479 Ni 2 1 H 3 do. f 480 Ni 1 2 4 -S03H 3 -NH (CHE2) 3N- f CH3

Example 481

  In 150 parts of water, 1.8 parts of sodium nitrite are stirred with 25.5 parts of the compound prepared according to known methods by sulfochlorination of nickel phthalocyanine and then reaction with 1,3-diaminobenzene-4- acid. sulfonic acid, and containing per molecule an average of about 2.5 sulfo groups and 1 sulfonamido group. This solution is cooled to 0-20 and added dropwise to 100 parts of an ice-water mixture and 12 parts of hydrochloric acid.

  %. Then the suspension of the diazo-

  resulting solution to a solution comprising 5.9 parts

  1- (3'-methylamino-propyl) -6-hydroxy-4-methylpyri-

  done- (2) in 300 parts of an ice / water mixture, all

  keeping the temperature at 0-50. During copulation

  the pH of the mixture is maintained at 9-9.5 by

  30% sodium hydroxide solution. A green solution is obtained which is reacted with cyanuric chloride, then with 1, 2-diaminopropane and then with 5-cyano-2,4,6-trichloropyrimidine, proceeding as described in Example 473. which gives (LZu) a (9gZl) saInuao; twelfth quepuodea SAE2 'sauTue DotIqlqd healthy, p iaaedaid Inad uo T8b aTdwxali e IT2ap amUoD quepgooad us 61S e Z8b saIdmaxs gITlnow not sgPTpIos sauallaDxa p qe aaiunI el e sGaAaTI sat4pTIos sap lueluasaid sainjuTaq Sad' alueiTaq Alaa aDuenu aun ua uoloo aT laTInDTIaed ua qa AsoInTiaD ap saaqT 5st; u QUT II úELb eTdwexs, W = azap eumoD quvpgooad ua aiOST uo, T anb

HDHN ID -

-N "(HD)

  b; eine n oou ap easodpoD o00 OOl 1NO 59Zú9Zc 1 01

S 03H), .. 3

  MePcR _CH CN Cl NN 3 12, C H CNC l -wherein the symbols are as defined in

V 0SO3H) 2-3

MePc R R1R

Tables 26 and 27 below.

  N CN Cl-in which the symbols are as defined in

Tables 26 and 27 below.

  The compounds of Examples 482 to 519 dye

  cotton in a green shade that is also brilliant

  when applying nickel phthlocyanine.

  These dyes have excellent fastness to

light and wet.

102 2632651

  Table 25 / ComDos $ s of formula (T26)

Ex. No. Me R Q3 -B2-NR1- - W -

482 Cu SO3H H - (CH2) 3N- -NHCH2CHNH-

CH3 CH3

483 Ni H H do. do.

484 Ni H -CONH2 do. do.

485 Ni SO3HH - (CH2) 3NH- do.

486 Cu do. H-CH 2 CH 2 NH-do.

487 Ni do. H do. -NH (CH2) 3N

CH3

488 Ni do. -CONH 2 - (CH 2) 3 NH-d 2

489 Ni do. H do. do.

490 Ni do. H - (CH2) 3N- do.

CH3

491 Ni do. H do. -NHCH2CHCH2NH-

I OH

492 Cu H H do. do.

493 Ni SO3H -CONH2 do. do.

494 Ni do. H-CH 2 CH 2 NH-do.

495 Ni S03HH - (CH2) 3N- -N N-

CH3

496 Cu H -CONH 2 do. -NHCH2CH2NH-

497 Ni SO3H H do. -N "- CH2CH2NH-

  498 Ni do. H - (CH2) 3NH- -NH (CH2) 3NH-

103 2632651

  Table 27 / Compounds of formula (T27) position of

Ex.No. R Ril R12 R9 -NH- - W -

499 Cu SO3H OH CH3H5 -NHCH2CHNH-

I CH3

500 Ni do. OH do. H 5 do.

501 Ni do. NH2 do. H 5 do.

502 Ni H OH do. 2-SO3H 5 do.

503 Ni SO3H OH -COOH H 4 do.

504 Cu do. OH CH3H5 -NH (CH2) 3N-

CH3

505 Ni do. OH do. 2-S03H 5 do.

506 Ni do. OH do. H 4 do.

507 Cu do. ## STR2 ##

508 Ni OH CH3 2-SO3H 5 do.

  509 Ni H OH do. do. 5 -NHCH2CHCH2NH-

OH -

510 Ni S03H OH do. H 4 do.

511 Cu do. OH do. 2-SO3H 5 do.

512 Ni do. NH2 do. do. 5 do.

513 Ni do. OH do. do. 4 -N N-

514 Cu do. OH do. H 5 -N NCH2CH2NH-

  515 Ni H OH -COOH H - 5 -NHCH2CH2NH-

516 Cu H OH CH 3 H 4

517 Ni SO3H OH do. H 5 do ..

518 Ni do. NB2 do. H 4 do.

  519 Ni do. OR do. 2-S03H 5 -NH (CH2) 3NH-

2632651 '

Example 520

  By proceeding as described in Example 481 and using the appropriate starting materials, the compound of the formula ## STR2 ## can be prepared in a bright green shade. . The dyes obtained have good fastnesses to the

light and wet.

  By proceeding according to the methods described above, the compounds of Examples 1 to 520 are obtained in the form of sodium salt. Depending on the reaction and isolation conditions, or by reaction of the sodium salts according to known methods, the compounds can also be obtained in free acid form or in the form of other salts, for example in the form of a salt containing 1 or more of the cations indicated in the

this description.

  Application Example A 0.3 part of the compound of Example 1 is dissolved in 300 parts of demineralised water and 15 parts of sodium sulfate (calcined) are added. The dye bath was heated to 40 and then parts of a cotton (bleached) fabric were added. After 30 minutes at 40, a total of 6 parts of sodium carbonate are added to the bath in portions and every 10 minutes.

  sodium (calcined) as follows: 0.2, 0.6, 1.2 and finally

  4.0 parts. During the addition of the sodium carbonate, the temperature is maintained at 40 ° C. We continue

  the dye for another 1 hour to 40.

  The dyed fabric is then rinsed with cold water for 3 minutes and with hot water for another 3 minutes. The substrate is boiled for 15 minutes in 500 parts of demineralized water in the presence of 0.25 part of a commercially available anionic detergent. After rinsing with hot water (for 3 minutes) and centrifugation, the substrate is dried in a dryer at about 700. An orange dye is obtained on the cotton having good

  light and wet fastness and is resistant to

aunt to oxidizing agents.

  Application Example B To a dye bath containing 300 parts of demineralized water, 10 parts of sodium sulphate (calcined) and 10 parts of a cotton (bleached) fabric are added. The bath is heated to 40 over 10 minutes and 0.5 part of the compound of Example 1 is added. After another 30 minutes at 40, 3 parts of sodium carbonate (calcined) are added and keep on going

  the dye at 40 for another 45 minutes.

  The dyed fabric is rinsed with hot water and then with cold water and is washed at the boil according to the method indicated in application example A. After rinsing and drying, a dyeing is obtained

  orange on cotton, which has similar solidities

  those indicated in application example A. Application example C

  The procedure is as described in the example of application

  cation A, but using 0.3 part of the compound of Example 481 and instead of a total of 6 parts of sodium carbonate added in portions, is added in one portion 2 parts of calcined sodium carbonate. The starting temperature of 400 is increased to 60 and the dyeing is carried out for another hour at 60.degree. For the remainder, the procedure is as described in application example A. A bright and intense green dye is obtained on the cotton and which presents

  very good fastness to light.

  Application Example D 2.5 parts of the compound of Example 473 are dissolved in 2000 parts of water. 100 parts of a cotton fabric are added and the temperature is raised

  from the dye bath to 80 within 10 minutes.

  100 parts of sodium sulphate (calcined) are added and, afterwards, 20 parts of sodium carbonate (calcined) are added. Dyeing is continued for 1 hour at. The dyed fabric is then rinsed with cold water and then with hot water, and is washed at the boil according to the method indicated in application example A. After rinsing and drying, a bright turquoise dye is obtained on cotton, which presents

good solidity.

  The compounds of the other examples or mixtures of compounds of the examples can also be used for dyeing the cotton according to the method described in application examples A to D. Application example E By following the usual printing methods, it is applied on a cotton fabric a printing paste comprising parts of the compound of Example 1 parts of urea 350 parts of water 500 parts of a thickener based on 4% sodium alginate and parts of sodium bicarbonate 1000 parts The printed fabric is dried and fixed at 102-104 for 4-8 minutes. It is rinsed cold and then hot, and is washed at boiling point (according to the method described in application example A).

  and dry it. An orange print is obtained first

  feeling good general solidities.

  The compounds of Examples 2 to 520 or mixtures of compounds of the examples can also be used to print the cotton according to the method

  described in application example E. All the impres-

  obtained have good solidity.

Claims (13)

  1. A compound of formula I Ci F X-N-Alk N <c i I R R N to CN Cl b in which   Fc means the remainder of a hydrosoluble dye   selected from azo dyes, from   formazane, phthalocyanine, azo   methine, oxazine, thiazine, phenazine and triphenylmethane, in non-metallized or metallized form, said residue may also contain a reactive group, each a means, independently, 0 or 1, b is 1 or 2, each X independently means a direct bond, -CO- or -SO 2 -, each R 1 independently means hydrogen or an unsubstituted or monosubstituted C1-C4 alkyl group by a halogen or a hydroxy group, -SO3H , -OSO3H or COOH,   each Alk independently means an alkyl group   in C2-C4, and each W independently means a remainder -N-Bi - N-, -N N- R1 R1   -N- (C1-C4 alkylene) -alkyl-C4-NN-alkylene (C1-C4) I - R1 R1   N, << 0 or -N N i - N - \ - J or (So3H) M (SO3H) 3 3 wherein m is 0 or 1 and -'-   B1 means a C2-C6 alkylene group optionally   optionally interrupted by -O- or -NR1-, a C3-C6 alkylene group which is substituted by one or two hydroxy groups or a carboxy group, or a residue R2 R2   wherein n - is 0, 1, 2, 3 or 4 and R 2 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, -COOH or -SOaH, and mixtures of compounds of formula I,   in free acid form or in salt form.   2. A compound according to claim 1,   characterized in that each W means, independently a rest -N- Bîb-N- or -N N-   R 1b Rbbbbb denotes a C 2 -C 3 alkylene group, C 3 -C 4 alkylene group substituted by a hydroxy group, or a residue - (CH 2) n aO (C 2 n R 2b R2b in which R 2b means hydrogen or -SO3H, and n2 is 0, 1 or 2, and each R1b independently means hydrogen or   methyl, ethyl or 2-hydroxyethyl group.   3. A compound according to claim 1, characterized in that the compound is non-metallized and corresponds to the formula r (Z) b (1). LDK - N = N -   wherein DK means the remainder of a benzene or naphthalenic diazotizing component, KK means the remainder of a benzene, naphthalenic or heterocyclic coupling component, or the remainder of an acidic CH compound capable of being enolized, Z means Cl ci CN CI   W is as defined in claim 1, and b is 1, Z being bonded to the diazotization component or the coupling component by a group -N (R1) - in   R1 is as defined in claim 1.   4. A compound according to claim 3, characterized in that it corresponds to the formula R.sub.N = X7a (SO 3 H) .sub.r (SO 3 H) in which R.sub.b is hydrogen or a methyl, ethyl or 2-hydroxyethyl group. Z. means N W1 CN Cl wherein W1 means a remainder   -N- B, -N-, -N N-, -N- (C 2 -C) alkylene-N N- Rib RIb Rlb 112 2632651 or -N N -alkylene at 0-C3)   RIb in which Rlb has the meaning given above, l b B1. signifies C 2 -C 4 alkylene, - (C 2 -C 3) alkylene-O- (C 2 -C 3) alkylene -, - (C 2 -C 3) alkylene-N (R 1b) - (C 2 -C 3) alkylene - C3-C4 alkylene monosubstituted with a hydroxyl group or a residue - (CH2) n9 n R2a R2 where RIb has the meaning given above, n1 means 0, 1, 2 or 3, R28 means hydrogen or a methyl, methoxy, -COOH or -SO3H, m is 0 or 1, r is 1 or 2, and m + r is 2 or 3, R6 is hydrogen or methyl or methoxy, and R7a is hydrogen , chlorine or a group   methyl, methoxy, -NHCOCH3 or -NHCONH2.   5. A compound according to claim 3, characterized in that it corresponds to the formula ## STR2 ## 3 4 SOH   Wherein each R1b, independently, is as defined in claim 4, Z, is as defined in claim 4, a is 0 or 1, the sulfo group is located at the 3- or 4-position of the naphthalenic ring, and DK3 is a radical of formula (a2) or (c2) SOH R4 in which R3. and R4. mean,   3a R4a independently of each other, the hydro-   (a2) gene, chlorine or a methyl, methoxy, ethoxy or -COOH group, wherein m is O or 1, p is 0, 1 or 2, and / S0H (m + p is 1 or 2.   (S03H) p (03H) m (c2) 6. A compound according to claim 1, characterized in that the compound is unmetallized and corresponds to the formula -t (2) RR X N = N 4 N = N N Z (2) R R R1 7. x- (S03H) t in which-   Z is CN and R are as defined in claim 1, t is 2 or 3, R 6 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, R 1 means hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, -NHCO (C1-C4alkyl) or NHCONH2, R6x, independently of R6, has one of the meanings of R6 and R7, regardless of R7, has one of the meanings of R7.   7. A compound according to claim 1,   characterized in that the compound is a metal complex   lifer which, in non-metallized form, corresponds to formula (3a) or (3b), OH R - Z A-N = N (3a) SO R S3H (SO3H) m R22 OH N O HO S N N 3 3 - -f 503 H (3b) S03H NR 1-Z   in which Z is CN 4 / N CN Cl R 1 and W are as specified in claim 1, A signifies a remainder ll R22 R22 or R17H H (S3H) m (SO3H) q R22 HOS X " - O R17 (S03H)   or 3 each m means, independently, 0 or 1, q is 1, 2 or 3, -   R17 is hydrogen, halogen, nitro, C1-C4 alkyl, C1-C4 alkoxy, -COR13, -SO3 H or -NHCOCH3, R22 is OH, OCH3 or NH2, and R13 is OH, a group -O-C 1 -C 4 alkyl or NH 2, said metalliferous complex being a 1: 1 complex of copper or a symmetrical or asymmetric 1: 2 complex of chromium or cobalt,   as a free acid or a salt.   8. A compound according to claim 1, characterized in that it meets the formula > S03H) c.   Wherein c is 1, 2 or 3, and d is 0, 1 or 2,   with the condition that c + d is not.   greater than 3, Z means Cl CN Cl   each Ri, independently, and W are as specified   in accordance with claim 1, Pc means the phthalocyanine residue, Me means copper, nickel, cobalt, iron or aluminum,   each R24 and R25 independently means hydrogen.   C1-C6alkyl or -NR24R25 is a 5- or 6-membered saturated heterocycle which may further contain -O- or -N (R31) - where R31 is hydrogen   or a C1-C4 alkyl, 2-hydroxy-   ethyl or 2-aminoethyl, R26 is hydrogen, halogen or hydroxy, C1-C4 alkyl, C1-C4 alkoxy, -COOH or -SO3H, a is 0 or 1,   X4 means a divalent aliphatic bridge, arable   lipase or heterocyclic, said bridge optionally containing -N (R1) -, or means -N-N-KK2 wherein KK2 means R R Q2   (B) -3 to HO 2 R 2 a B-Q 2 the carbon atom marked with an asterisk indicating the position where the coupling occurs, R 11 is -OH or NH 2, R 12 is C 1 -C 4 alkyl or -COR1 3   R13 is -OH, -O-C1-C4alkyl or -NH2, Rg9 is hydrogen, halogen or C1-C4alkyl, C1-C4alkoxy, -COOH OR -SO 3 H,   a is as defined above, B3 is a divalent bridge, Q2 is hydrogen, C1-C4 alkyl, C5-C6 cycloalkyl, phenyl or phenyl-C1-C4 alkyl in which the phenyl ring optionally bears from 1 to 3 substituents chosen from halogens and C 1 -C 4 alkyl, C 1 -C 4 alkoxy, -COOH and -503H groups, -COR 13 group or C 1 -C 4 alkyl group monosubstituted by 503H, - OS03H or -COR1 3,   Q3a is hydrogen, -CN, -SO3H, -COR13, C1-C4alkyl, C1-C4alkyl monosubstituted with halogen or hydroxy, CN, C1-C4alkoxy, R9, -S03H, -OS03H or -NH2, or a group -SO2NH2, R9 R   R 15 d9 or -Ene. Ane, in which R1 s is hydrogen, C1-C4 alkyl or C2-C4 hydroxyalkyl, AnQ is non-chromophore anion, and R9 and R13 are as defined above, and B2 is C2 alkylene; -C6, a C3-C6 alkylene group monosubstituted with a hydroxyl group, a C2-C6 alkylene group interrupted by -O- or NR1-, or a C1-C4 alkylene moiety; (S03H) (SO 3H)   3m 3m alkylene in Cl-C4) - o R1 and m are such cue   _ a] kln e n0] -C- defined in the claim   (S03H1) tion 1, or -B2 - NR1 - (Z) signifies a residue - (C2-C4 alkylene) - N N - (Z),   and mixtures of compounds of formula (7).   9. A process for preparing a compound of formula I as defined in claim 1 and mixtures of compounds of formula I, characterized in that a compound of formula II FL XN-Alk N is reacted. Where Y3 is chlorine or -WH, and Fc, X,   R1, Alk, a, b and W are as specified for claiming   1, or a mixture of compounds of formula II,   when Y3 signifies -W-H, with 5-cyano-2,4,6-tri-   chloropyrimidine or, when Y3 signifies chlorine, with a compound of formula III H-W Cl III CN CI   wherein W is as defined in claim   1, using a 1: 1 molar ratio for the compounds Formula II and III.   10. The use of the compounds according to one   any of claims 1 to 8, and mixtures of   these compounds as reactive dyes for dyeing or printing substrates containing hydroxy groups or nitrogen.   11. The use of the compounds according to one   any of claims 1 to 8, and mixtures of   these compounds as reactive dyes for dyeing or the printing of cotton.   12. Substrates containing hydroxy groups or nitrogen, characterized in that they have been dyed or printed with a compound according to   any one of claims 1 to 8, or a mixture of these compounds.   13. The cotton, characterized in that it has been dyed or printed with the aid of a compound according to any one of claims 1 to 8, or a mixture of these compounds.