PROCESS FOR THE MANUFACTURE OF FIBRE-REACTIVE PHTHALOCYANINE AZO DYESTUFFS

PROCEDE D'OBTENTION INDUSTRIELLE DE COLORANTS AZOIQUES DE PHTALOCYANINE, REAGISSANT AVEC LES FIBRES

English Abstract

Abstract of the Disclosure
Fiber reactive phthalocyanine azo dyes having at least one
group of the formula
<IMG>
wherein ar and B denote divalent aromatic or araliphatic
radicals, R3, R4 and R7 denote hydrogen or optionally
substituted alkyl radicals and A denotes a fiber reactive
radical, are prepared by diazotizing phthalocyanine amines
having at least one group of the formula
<IMG>
wherein the amino group is linked to an aromatic C atom of
the radical ar, coupling the diazonium compound with a
succinic acid derivative of the formula V
<IMG> (V)
wherein Z denotes hydrogen or an optionally substituted
hydrocarbon radical , treating the hydrazone intermediate
with alkali to obtain a phthalocyanine pyrazolone having
at least one group of the formula

<IMG>
and coupling this product with a diazotized amine of the
formula
<IMG>
wherein the amino group is linked to an aromatic C atom
of the radical B.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for the manufacture of water-soluble fibre-
reactive phthalocyanine azo dyestuffs of the formula I
<IMG> I
wherein A is a fibre-reactive radical, B is a radical of a
mononuclear or dinuclear, aromatic hydrocarbon or araliphatic
hydrocarbon the alkylene chain of which is bonded to the <IMG> group,
which is optionally substituted by one -SO3H group and each
nucleus being optionally further substituted, by alkoxy having
1-4 C atoms, -SO2R? or an additional -SO3H group, by one or two
identical or different substituents selected from halogen,
<IMG> or -COOH or by one to three identical or different
alkyl radicals having 1-4 C atoms, R? denoting hydrogen, methyl,
carboxymethyl, sulphomethyl, an alkyl radical having 2-6 C atoms
which is optionally substituted by Cl, Br, OH, alkoxy, alkanoyl,
amino or alkanoyloxy each having 1-6 C atoms, -COOH or -SO3H,
a phenylalkyl or naphthalkyl radical having 1-3 C atoms in the
aliphatic chain, or phenyl or naphthyl, the aromatic nuclei
being optionally substituted or further substituted by one or
more of Cl, Br, OH, alkyl and/or alkoxy each having 1-6 C atoms,
alkanoylamino having 1-6 C atoms, -COOH or SO3H, R? denoting
hydrogen, methyl, carboxymethyl, sulphomethyl, and alkyl radical
67

having 2-6 C atoms which is optionally substituted by Cl, Br,
OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms,
benzoylamino, alkanoyloxy having 1-6 C atoms, -COOH or -SO3H or
an unsubstituted alkyl radical having 7-20 C atoms, R6 denoting
methyl, carboxymethyl, alkyl having 2 or 3 C atoms, benzyl or
phenyl, the aromatic nuclei being optionally monosubstituted or
disubstituted by -COOH or -SO3H,
Pc is the radical of a metal-containing or metal-free phthalo-
cyanine, ar is the radical of a mononuclear or dinuclear, aromatic
hydrocarbon or araliphatic hydrocarbon the alkylene chain of
which is bonded to the <IMG> group, which is optionally substituted
by a -SO3H group and each nucleus being optionally further substi-
tuted by alkoxy having 1 to 4 C atoms, -SO2-R6 or additional
-SO3H group, by one or two identical or different substituents
selected from halogen, <IMG> and -COOH, or denotes a phenylene
radical which is optionally substituted by a -SO3H group and which
can be additionally substituted by one to three identical or
different alkyl radicals having 1-4 C atoms, R1 and R? can be the
same or different and each represents hydrogen, methyl, carboxy-
methyl, sulphomethyl, an alkyl radical which contains 2-6 C atoms
and which is optionally substituted by Cl, Br, OH, alkoxy having
1-6 C atoms, alkanoylamino having 1-6 C atoms, alkanoyloxy having
1-6 C atoms, -COOH or -SO3H, a phenalkyl or naphthalkyl radical
having 1-3 C atoms in the aliphatic chain or phenyl or naphthyl,
the aromatic nuclei being optionally substituted or further
substituted by one or more of Cl, Br, OH, alkyl and/or alkoxy each
having 1-6 C atoms, alkanoylamino having 1-6 C atoms, -COOH or
-SO3H, R2 and R2 can be the same or different and denote hydrogen,
methyl, carboxymethyl, sulphomethyl, an alkyl radical which
contains 2-6 C atoms and is optionally substituted by Cl, Br,
OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms,
68

benzoylamino, alkanoyloxy having 1-6 atoms, -COOH or -SO3H,
or an unsubstituted alkyl radical having 7-20 C-atoms,
R3 is hydrogen, methyl, carboxymethyl, sulphomethyl, or an
alkyl radical which contains 2-6 C atoms and is optionally
substituted by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoyl-
amino having 1-6 C atoms, benzoylamino, alkanoyloxy having
1-6 C atoms, -COOH or -SO3H,
69

R4 is hydrogen, alkyl having 2-6 C atoms substituted by Cl, Br,
OH or alkoxy having 1-4 C atoms, or unsubstituted alkyl having
1-18 C atoms,
R6 is methyl, carboxymethyl, alkyl having 2 or 3 C atoms, or
benzyl or phenyl, the aromatic nuclei being optionally monosub-
stituted or disubstituted by -COOH or SO3H,
R7 is hydrogen, methyl, carboxymethyl, sulphomethyl or an alkyl
radical having 2-4 C atoms which is optionally substituted by
Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having
1-6 C atoms, benzoylamino, alkanoyloxy having 1-6 C atoms, -COOH
or -SO3H,
k is 0, 1, 2 or 3, q represents 0, 1 or 2 and m represents 1,2,
3 or 4 and the sum of k, q and m is 3 or 4, or an alkali metal,
ammonium or alkaline earth metal salt thereof, in which process:
(a) an amine of the phathalocyanine series of the general
formula
<IMG> II
in which the amino group substituent on the ar radical is bonded
to an aromatic C atom of said radical ar and wherein Pc, ar, R1,
R2, R3, k, q and m have the same meaning as defined above, in
formula I, is diazotised and coupled in an aqueous medium at a
pH value between 3 and 8 with a succinic acid derivative of the
formula III
<IMG>

wherein R'4 and R5 are the same or different and each is alkyl
having 2-6 C atoms substituted by Cl, Br, OH or alkoxy having
1-4 C atoms, or unsubstituted alkyl having 1-18 C atoms, and Z
denotes hydrogen, alkyl having 1-10 C atoms optionally substi-
tuted by alkoxy having 1-4 C atoms, or alkoxycarbonyl having
2-6 C atoms, a phenyl radical optionally substituted by
Cl, Br, or alkyl or alkoxy having 1-4 C atoms, or alkoxy-
carbonyl having 2-6 C atoms, so as to form a hydrazone of the
formula IV
<IMG> IV
wherein Pc, ar, R1, R2, R3, R4, k, q and m have the same
meaning as defined above in formula I and R5 has the same
meaning as defined above in formula III,
(b) The compounds of formula IV is converted by the action
of an alkali into a pyrazolone of the general formula V
<IMG> V
wherein Pc, ar, R1, R2, R3, R4, k, q and m have the same
meaning as defined above in formula I; and
71

(c) The pyrazolone of formula V is coupled with the diazonium
compound of an amine of the general formula VI H2N-B-W wherein
B has the same meaning as defined in formula I and W is a group
of the formula -N(R7)A, wherein R7 and A have the same meaning
as defined above in formula I, or a precursor of said group
-N(R7)A; and when W is said precursor it is subsequently converted
to said group of the formula -N(R7)A; so as to produce said
dyestuff compound of the formula I.
2. A process as claimed in claim 1 wherein R1 and/or R? is
alkyl having 2 to 6 carbon atoms and substituted by acetylamino,
benzoylamino or acetoxy.
3. A process as claimed in claim 1 wherein, in the amine of
formula II, Pc is the radical of cobalt phthalocyanine, copper
phthalocyanine or nickel phthalocyanine,
4. A process as claimed in claim 1 wherein Pc is the radical
of nickel phthalocyanine.
5. A process as claimed in claim 1 wherein, in the amine of
formula II, ar is a phenylene mono-methylene-phenylene or poly-
methylene-phenylene radical of the general formula
<IMG>
wherein n denotes an integer from 1 to 10, or naphthylene or
monomethylene-naphthylene or polymethylene-naphthylene radical
of the general formula
<IMG>
wherein n denotes an integer from 1 to 3, or an optionally
substituted radical of the formula
72

<IMG> , <IMG> , <IMG>
<IMG> , <IMG> , <IMG>
<IMG> or <IMG>
optionally substituted as given in claim 1.
6. A process as claimed in claim 5, wherein in the amine
of formula II, ar is a phenylene or naphthylene radical or
an optionally substituted radical of the formula
<IMG>
or <IMG>
optionally substituted as given in claim 1.
7. A process as claimed in claim 1, wherein, in the amine
of formula II, ar is a phenylene radical which is optionally
substituted by one or two carboxyl groups or by one or two
sulpho groups, or a naphthyl radical which is substituted
by one or two sulpho groups, or a stilbenylene radical which
is substituted by one or two sulpho groups.
73

8. A process as claimed in claim 7, wherein in the
amine of formula II ar is a radical of the formula
<IMG> , <IMG> , <IMG> , <IMG> , <IMG> ,
<IMG> or <IMG>
9. A process as claimed in claim 1 wherein, in the amine of
formula II, R1 and R? are the same or different and each is
hydrogen, alkyl having 2 or 3 C atoms, optionally substituted
by OH, alkoxy having 1-3 C atoms, -COOH or SO3H, methyl,
carboxymethyl or sulphomethyl.
10. A process as claimed in claim 1 wherein, in the amine
of the phthalocyanine series of the formula II, R2 and R? are
the same or different and each is hydrogen, methyl, carboxy-
methyl, alkyl having 2 or 3 C atoms, optionally substituted
by OH, alkoxy having 1-3 C atoms, -COOH or -SO3H, or
unsubstituted alkyl having 1-20 C atoms.
11. A process as claimed in claim 10 wherein R2 and R?
are the same or different and each is hydrogen, methyl,
carboxymethyl or alkyl having 2 or 3 C atoms optionally
substituted by OH.
12. A process as claimed in claim 1 wherein R1 and R2
as well as R? and R? are the same or different and each is
hydrogen, methyl or .beta.-hydroxyethyl.
74

13. A process as claimed in claim 1 wherein, in the amine
of formula II, R3 is hydrogen, methyl, carboxymethyl, sulpho-
methyl or an ethyl radical which is optionally substituted by
Cl, OH, alkoxy having 1 or 2 C atoms, -COOH or -SO3H.
14. A process as claimed in claim 1 wherein, in the amine of
the phthalocyanine series of the formula II, q is 0, k is 2 or 3
and m is 1 or 2 and the sum of k + m is 4.
15. A process as claimed in claim 1 wherein, in the amine of
formula II, the substituents on the Pc radical are in the 3-Posi-
tions and/or 4-positions of the phthalocyanine.
16. A process as claimed in claim 15 wherein the substituents
on the Pc radical are in the 3-positions of the phthalocyanine.
17. A process as claimed in claim I wherein R4 denotes ethyl
substituted by Cl, OH or alkoxy having 1-2 C atoms, or unsubstituted
alkyl having 1-6 C atoms.
18. A process as claimed in claim 1 wherein R5 is ethyl
substituted by Cl, OH or alkoxy having 1-2 C atoms, or unsubstituted
alkyl having 1-18 C atoms.
19. A process as claimed in claim 1 wherein R4 and R5 are
identical and denote methyl or ethyl.
20. A process as claimed in claim 1 wherein Z denotes hydrogen,
alkyl having 1-3 C atoms, phenyl, methyl-phenyl or alkoxycarbonyl
having 2 or 3 C atoms.
21. A process as claimed in claim 20 wherein Z denotes methyl.
22. A process as claimed in claim 1 wherein, in the diazonium
compound of the amine of the general formula VI, A is a fibre-
reactive radical which contains a radical which can be split off
as an anion or as a neutral radical or an activated double
bond which is capable of an addition reaction.

23. A process as claimed in claim 1 wherein R? is alkyl
having 2 to 6 carbon atoms substituted by acetylamino, benzoyl-
amino or acetoxy.
24. A process as claimed in claim 1 wherein, in the diazonium
compound of the amine of the general formula VI, A is the radical
of an aliphatic carboxylic or sulphonic acid which contains a
substituent which can be easily nucleophilically replaced; or is
an .alpha.,.beta.-unsaturated aliphatic carboxylic or sulphonic acid; or is
the radical of an aliphatic carboxylic or sulphonic acid which
is easily convertable to the radical of an .alpha.,.beta.-unsaturated
aliphatic carboxylic or sulphonic acid with the splitting off of
a neutral or anionic group.
25. A process as claimed in claim 1 wherein, in the diazonium
compound of the amine of the general formula VI, A is the radical
of a heterocyclic carboxylic or sulphonic acid which contains a
substituent which can be easily nucleophilically replaced.
26. A process as claimed in claim 1 wherein, in the diazonium
compound of the amine of the general formula VI, A is the
radical of a six-membered heterocyclic compound having 2 or 3 N
atoms and at least one substituent which can be easily nucleophili-
cally replaced.
27. A process as claimed in claim 26 wherein said six-member
heterocyclic compound additionally has a non-labile substituent
which in turn contains no fibre-reactive radical having a radical
which can be split off as an anion or as a neutral radical or an
activated double bond which is capable of an addition reaction.
28. A process as claimed in claim 1 wherein A is the radical
of s-triazine.
76

29. A process as claimed in claim 26 wherein said six-
membered heterocyclic compound additionally has a non-labile
substituent of the general formula -Het-BR-Het'-A' wherein
Het and Het' are the same or different and each is an oxygen
or sulphur atom or a <IMG>, <IMG> or <IMG> group,
Br is a divalent aliphatic, aromatic or araliphatic radical
and A' has the same meaning as any of the values given for A.
30. A process as claimed in claim 1, wherein, in the
diazonium compound of the amine of the general formula VI,
B is phenylene, monomethylene-phenylene or polymethylene-
phenylene radical of the general formula
<IMG>
wherein n denotes an integer from 1 to 10, or naphthylene or
monomethylene-naphthylene or polymethylene-naphthylene radical
of the general formula
<IMG>
wherein n denotes an integer from 1 to 3, or an optionally
substituted radical of the formula
<IMG>
<IMG> or <IMG>
optionally substituted as given in claim 1.
77

31. A process as claimed in claim 1 wherein B is an
optionally substituted phenylene or naphthylene radical
or a radical of the formula
<IMG>
or <IMG>
optionally substituted as given in claim 1.
32. A process as claimed in claim 1 wherein B is a
phenylene radical optionally substituted by one or two
carboxyl groups or by one or two sulpho groups, or a naphthyl
radical which is substituted by one or two sulpho groups or a
stilbenylene radical which is substituted by two sulpho groups.
33. A process as claimed in claim 32 wherein B is a radical
of the formula
<IMG> , <IMG> , <IMG> , <IMG> , <IMG> ,
<IMG> or <IMG>
34. A process as claimed in claim 1 wherein, in the diazonium
compound of the amine of the general formula H2N-B-W, W is a
group of the formula <IMG>, R7 having the same meaning as
78

defined above and "acyl" being an aliphatic acyl group having
1 to 3 C atoms, or a benzoyl group, and after coupling of said
amine of the general formula H2N-B-W to the pyrazolone of the
formula V, the resulting phthalocyanine azo dyestuff is saponi-
fied and the resulting dyestuff of the formula Ia
<IMG> Ia
wherein B, Pc, ar, R1, R2, R3, R4, R7, k, q and m have the same
meaning as defined above in formula I, is acylated with an
acylating agent of the formula X-A, wherein A has the same
meaning as defined above in formula I and X is a leaving group.
35. A process as claimed in claim 34 wherein said "acyl" is
acetyl or unsubstituted benzoyl.
36. A process as claimed in claim 1 wherein in die diazonium
compound of the amine of the general formula H2N-B-W, W is a
nitro group and after coupling of said amine of the general
formula H2N-B-W to the pyrazolone of the formula Y, the resulting
phthalocyanine azo dyestuff is reduced and the resulting dye-
stuff of the formula Ib
<IMG> Ib
79

wherein B, Pc, ar, R1, R2, R3, R4, k, q and m have the same
meaning as defined above in formula I, is acylated with an
acylating agent of the formula X-A wherein X is a leaving group.
37. A process as claimed in claims 34 and 36 wherein X is a
group which can be split off by the nucleophilic attack of the
secondary or primary amino group, respectively, of the dyestuff
of formula Ia or Ib, respectively.
38. A process for the preparation of phthalocyanine azo
dyestuff compound of the general formula I as defined in claim 1
in which a hydrazone of the formula IV as defined in claim 1 is
converted by the action of an alkali into a pyrazolone of the
general formula V as defined in claim 1 and said pyrazolone of
formula V is coupled with the diazonium compound of an amine
of the general formula H2N-B-W as defined in claim 1 so as to
form the dyestuff compound of formula I.
39. A method of dyeing and printing a cellulose material,
cellulose-containing material, or a natural or synthetic poly-
amide material, wherein is used a compound prepared by a process
according to claim 1.

Description

The present invention relates to a process for themanufacture of valuable water-soluble fibre-reactive
phthalocyanine azo dyestuffs.
Thus, this invention provides for process for the
manufacture of water-soluble fibre-reactive phthalocyanine azo
dyestuffs of the formula I
( 3 )k
/ /R
Pc; _ (S2-N
q
\ ~ N=N- --B-N-A~
(S02-~ - ar-N ~ ~ R7
. wherein A is a fibre-reactive radical, B is a radical of a
~ mononuclear or dinuclear, aromatic hydrocarbon or araliphatic
: 10 hydrocarbon the alkylene chain of which is bonded to the -N-A
: 7
group, which is optionally substituted by one -S03H group and
each nucleus being optionally further substituted, by alkoxy
having 1-4 C atoms, -S02R6 or an additional -S03H group, by one
or two identical or different substituents selected from halogen,
-S02N\ 1 or -COOH or by one to three identical or different
R2
alkyl radicals having 1-4 C atoms, Rl denoting hydrogen, methyl,
carboxymethyl, sulphomethyl, an alkyl radical having 2-6 C atoms
which is optionally substituted by Cl, Br, OH, alkoxy, alkanoyl,
amino or alkanoyloxy each having 1-6 C atoms, -COOH or -S03H,
a phenylalkyl or naphthalkyl radical having 1-3 C atoms in the
aliphatic chain, or phenyl or napthyl, the aromatic nuclei
being optionally substituted or further substituted by one or
more of Cl, Br, OH, alkyl and/or alkoxy each having 1-6 C atoms,
~' ..

B~9
alkanoylamino having 1-6 C atoms, -COOH or S03H, R2 denoting
hydrogen, methyl, carboxymethyl, sulphomethyl, and alkyl radical
R4 is hydrogen, alkyl having 2-6 C atoms substituted by C1,
Br, OH or alkoxy having 1-4 C atoms, or unsubstituted alkyl
having 1-18 C atoms,
R6 is methyl, carboxymethyl, alkyl having 2 or 3 C atoms, or
benzyl or phenyl, the aromatic nuclei being optionally monosub-
stituted or disubstituted by -COOH or S03H,
R7 is hydrogen, methyl, carboxymethyl, sulphomethyl or an alkyl
radical having 2-4 C atoms which is optionally substituted by
Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having
1-6 C atoms, benzoylamino, alkanoyloxy having 1-6 C atoms, -COOH
or -S03H,
k is 0, 1, 2 or 3, q represents 0, 1 or 2 and m represents 1, 2,
3 or 4 and the sum of k, q and m is 3 or 4, or an alkali metal,
ammonium or alkaline earth metal salt thereof, in which process:
(a) an amine of the phathalocyanine series of the general
formula
( 3 )k
~Rl~
Pc _( so2--N J II
\ q
(S2-NI ar-NH2)m
R3
in which the amino group substituent on the ar radical is bonded
to an aromatic C atom of said radical ar and wherein Pc, ar, Rl,
R2, R3, k, q and m have the same meaning as defined above, in
formula I, is diazotised and coupled in an aqueous medium at a
pH value between 3 and 8 with a succinic acid derivative of the

1~95899
.~ formula III
R -OOC -CH f H-COOR4
CO-Z
wherein R'4 and R5 are the same or different and each is alkyl
having 2-6 C atoms substituted by Cl, Br, OH or alkoxy having
-. 1-4 C atoms, or unsubstituted alkyl having 1-18 C atoms, and Z
denotes hydrogen, alkyl having 1-10 C atoms optionally substi-
tuted by alkoxy having 1-4 C atoms, or alkoxycarbonyl having
2-6 C atoms, a phenyl radical optionally substituted by Cl,
; Br, or alkyl or alkoxy having 1-4 C atoms, or alkoxycarbonyl
having 2-6 C atoms, so as to form a hydrazone of the formula IV
(S03H) k
Pc / (~o -N' 1) IV
, \ 2 q R50-C- ICH2
(SO - N ar - NH-N = C
2 I COOR4)
wherein Pc, ar, Rl, R2, R3, R4, k, q and m have the same
meaning as defined above in formula I and R5 has the same
meaning as defined above in formula III,
(b) The compounds of formula IV is converted by the action
of an alkali into a pyrazolone of the general formula V
(SO3H)k
Pc / (SO -N' 1¦
R2
q ~H
(SO -N ar-N
2 R3 COOR4

~95~
' 1~ R2~ R3, R4, k, q and m have the same
meaning as defined above in formula I; and
(c) The pyrazolone of formula V is coupled with the diazonium
compound of an amine of the general formula VI H2N-B-W
wherein B has the same meaning as defined in formula I and
W is a group of the formula -N(R7)A, wherein R7 and A have
the same meaning as defined above in formula I, or a precursor
of said group -N(R7)A; and when W is said precursor it is
subsequently converted to said group of the formula -N(R7)A;
so as to produce said dyestuff compound of the formula I.
' In a further aspect of the invention there is
provided a method of dyeing and printing a cellulose material,
cellulose-containing material, or a natural or synthetic
polyamide material, wherein is used a compound prepared by
the process defined above.
In a still further aspect of the invention there
is provided a process for the preparation of phthalocyanine
azo dyestuff compound of the general formula I as defined
above in which a hydrazone of the formula IV as defined
20 above is converted by the action of an alkali into a pyrazolone
of the general formula V as defined above and said pyrazalone
of formula V is coupled with the diazonium compound of an
amine of the general formula H2N-B-W as defined above so as
to form the dyestuff compound of formula I.
Throughout the re~lainder of the aisclosure q is
referred to by the letter 1.
In the amines of the phthalocyanine series of the
general formula II to be employed according to the invention,

10~5899
Pc denotes, in particular, the radical of a metal-containing
phthalocyanine, ar denotes, in particular, the radical of a
. mononuclear or dinuclear aromatic or araliphatic hydrocarbon
; which is optionally substituted by a -S03H group and which can
be substituted in each nucleus by one substituent of the group
; alkoxy with 1-4 C atoms or -S02R6 or by an additonal -S03H
group, by one or two identical or different substituents of
- 4a -

1~9~899
: Rl
the groups halogen, -S02-N or -COOH or denotes a pheny-
~ R2
lene radical which is optlonally substituted by a -S03H group
and which can be additionally substituted by one to three
identlcal or dlfiere~t alkyl radlcals with 1-4 C atoms, Rl and
independently o~ one another denote, in particular, hydro-
gen, metbyl, carboxymothyl, ~ulphomethyl, an alkyl radical
with 2-6 C atoms whlch is optionally substltuted by Cl, Br,
OH, alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C atoms,
preierably acetylamino, benzoglamino, alkanoyloxy with 1-6 C
atomq, pre~erably acetyloxy, -COOH or -S03H, a phenalkyl or
naphthalkyl radical with 1-3 C atoms in the aliphatic chain,
phenyl or naphthyl, it being possible ~or the aromatic nuclei
to be substituted by Cl, Br, OH, alkyl and/or alkoxy with 1-6
C atoms, alkanoylamino wlth 1-6 C atoms, -COOH or -S03H, R2
and R 2 independently oi one another denote, in particular,
hydrogen, methyl, carboxymethyl, sulpbomethyl, an alkyl radi-
cal with 2-6 C atoms which is optionally substituted by Cl,
Br, OH, alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C
atoms, benzoylamino, alkanoyloxy with 1-6 C atoms, -COOH or
-S03H or an unsubstituted slkyl radical with 7-20 C atoms,
R3 denotcs, in particular, bydrogen, methyl, carboxymethyl,
sulphomethyl or an alkyl radical with 2-6 C atoms which 1~
optionally ~ubstituted by Cl, Br, OH, alkoxy with 1-6 C atoms,
alkanoylamino with 1-6 C atoms, b~nzoylamino, alkanoyloxy with
1-6 C atom~, -COOH or -S03H and R6 denote~, ln particular,
methyl, carboxymethyl, alkyl with 2 or 3 C atom~, benzyl or
phsnyl, it being poqslble ior the aromatic nuclei to be mono-
substituted or disubstituted by -COOH or -S03H.

lOgS899
The symbol k represents the numbers 0, 1, 2 or 3, 1
represents 0, 1 or 2 and m represents 1, 2,3 or 4 and the sum
o~ k, 1 and m is 3 or 4.
Amlnes oi the general i'ormula II w~ich are to be
employed according to the invention and in which Pc denotes
the radical oi a metal-contalning pbthalocyanine, such as, ~or
example, o~ cobalt or copper phthalocyanine, but i~ particular
the radical oi nickel phthalocyanine, are preierred.
Araliphatic radicals represented by ar are always bon-
ded to the -N~2 group with an aromatlc nucleus. ~ononuclear
aromatic or araliphatlc radlcals whlch can be represented by
ar are the optionally sub~tituted radicals phenylene and mono-
or poly-methylenephenylene o~ the general iormula
~ /
(~H2)n
in which n denotes an lnteger i'rom 1 to 10~
Dinuclear aromatic or araliphatic radicals whlch can
be represented by ar are the optionally substituted radicals
naphthylene, mono- or poly-methylenenaphthylene o~ the general
formula
(CH2)n ~t
in which n denotes an integer from 1 to 3, and the optionally
substituted radicals o~ the ~ormulae

1e~95899
'`' ' ' ' .
~, ~3Cil,-,~/, ~-CI~,,-CH
~Cll=C~I~ ~ ~ ~ ~li~
,. . .
CO ~ and ~ ~2 ~
Examples of mononuclear or dinuclear aromatic or arali-
-~ phatic hydrocarbon radicals which can be represented by ar in
the amines of the formula II are: 1,4-phenylene, 1,3-phenyl-
ene, 2-sulpho-1,4-phenylene, 3-sulpho-1,4-phenylene, 4- or 5-
sulpho-1,3-phenylene, 2-carboxy-1,4-phenylene, 3-carboxy-1,4-
phenylene, 4-, 5- or 6-carboxy-1,3-phenylene, 2-carboxy-5-
sulpho-1,4-phenylene, 2-carboxy-6-sulpho-1,4-phenylene, 3-
carboxy-6-sulpho-1,4-phenylene, 6-carboxy-4-sulpho-~3-phenyl-
ene, 5-carboxy-2-sulpho-1,3-phenylene, 2,5-dicarboxy-1,4-
phenylene, 4,6-dicarboxy-1,3-phenylene, 2-chloro-5-sulpho-1,4-
phenylene, 2-chloro-6-sulpho-1,4-phenylene, 3-chloro-6-sulpho-
1,4-phenylene, 6-chloro-4-sulpho-1,3-phenylene, 2-chloro-5-
carboxy-1,4-phenylene, 2,6-disulpho-1,4-phenylene, 2,5-disulpho-
- 1,4-phenylene, 4,6-disulpho-1,3-phenylene, ~-chloro-6-carboxy-
1,4-phenylene, 6-chloro-4-carboxy-1,3-phenylene, 4-chloro-5-
- carboxy-1,3-phenylene, 2-methyl-5-carboxy-1,4-phenylene, 2-
ethyl-6-carboxy-1,4-phenylene, 3-ethyl-6-sulpho-1,4-phenylene,
6-ethyl-4-carboxy-1,3-phenylene, 6-propyl-4-sulpho-1,3-
phenylene, 5-isopropyl-4-sulpho-1,3-phenylene, 5-isopropyl-6-

1~95~99
carboxy-1,3-phenylene, 4-n-butyl-6-sulpho-1,3-pheny~ene,
3-n-butyl-6-sulpho-1,4-phenylene, 4-tert.-butyl-6-sulpho-
1,3-phenylene, 3-isobutyl-6-sulpho-1,4-phenylene, 2,5-
diisopropyl-6-sulpho-1,4-phenylene, 2,4-diethyl-5-carboxy-
1,3-phenylene, 2,4,6-trimethyl-5-sulpho-1,3-phenylene, 2-
cyano-1,4-phenylene, 4-cyano-1,3-phenylene, 2-cyano-5-suipho-
1,4-phenylene, 2-trifluoromethyl-1,4-phenylene, 2-methyl-
sulphonyl-1,4-phenylene, 2-ethylsulphonyl-1,4-phenylene,
4-sulpho-1,5-naphthylene, 8-sulpho-1,5-naphthylene, 4-sulpho-
2,6-naphthylene, 2-carboxy-1,4-naphthylene, 2-carboxy-1,5-
naphthylene, 5-carboxy-1,4-naphthylene, ~-carboxy-1,8-
naphthylene, 3-carboxy-1,5-naphthylene, 4-carboxy-2,6-naphthyl-
ene, 4-carboxy-2,7-naphthylene, 1-sulpho-2,6-naphthylene, 8-
sulpho-1,3-naphthylene, 4,8-disulpho-2,6-naphthylene, 3,7-di-
sulpho-1,5-naphthylene, 1-sulpho-4-chloro-2,6-naphthylene, 1-
chloro-5-sulpho-2,6-naphthylene, 1-chloro-7-sulpho-2,6-naphthyl-
ene, 2-chloro-6-sulpho-1,4-naphthylene, 1-methyl-4-sulpho-
2,6-naphthylene and 2-methyl-'7-sulpho-1,4-naphthylene.
In each case, the hydrazone group is in the l-position of the
phenyl nucleus or in the l-position or 2-position of the
naphthalene nucleus. In the list which follows, examples
of compounds from which further divalent radicals which are
represented by ar are derived are indicated. The positions
of the two bonds with which the divalent radicals are bonded
on the one hand to the amino group (~irst position given) and
on the other hand to the group -N- (,econd position given) of
R3
the dyestuffs which can be manufactured according to the
-- 8 --
.

1~95~
invention are indicated in the second column of the table.
Compound from which -ar- is derived Position of the bonds
f -ar-
Diphenyl 4,4
2,2'-dimethyl-diphenyl 4,4
3,3'-dimethoxy-diphenyl 4,4
3,3'-dichloro-diphenyl 4,4
3,3'-dimethyl-diphenyl 4,4
2,2'-disulpho-diphenyl 4,4
diphenyl-et~hane 4,4
diphenyl ether 4,4
2,2'-disulpho-diphenyl-methane 4,4
2,2'-disulpho-diphenyl-ethane 4,4
3,3'-disulpho-diphenyl-ethane 4,4
2,2'-disulpho-diphenyl ether 4,4
2-sulphamido-diphenyl-ethane 4,4
2,2'-disulphamido-diphenyl-ethane 4,4
2,2'-di-~-hydroxyethylsulphamido-
diphenyl-ethane 4,4
stilbene-2,2'-disulphonic acid 4,4
methyl-phenyl 4,~
l-methyl-phenyl-3-sulphonic acid 4,~
l-ethyl-phenyl-2-sulphonic acid 4,~
l-propyl-phenyl-3-sulphonic acid 4,~
5-methyl-naphthalene-1-sulphonic acid 2,~
diphenylamine 4,4
6-methoxy-diphenylamine-2'-sulphonic
acid 3~4
4-methyl-diphenylamine-2'-sulphonic
acid 3,4

1(~95899
Compound irom which -ar- is derivedPosition of the bonds
oi -ar-
diphenylketone-5,5'-dlsulphonic acid 3,3'
diphenylketone-3'-sulphonic acid 3,4'
diphenylsulphone 4,4'
4,4'-dichloro-diphenylsulphone 3,3'
4,4'-disulpho-diphenylsulphone 3,3'
4-methyl-5-sulpho-diphenylsulphone 3,3'
In the amines oi the iormula II to be employed accor-
ding to the invention, the optionally substltuted radical~
phenylene, naphthylene,
-CH2 ~ ' -C~2-C~2 ~ , -CH2 ~ and ~ C~-CH
: are preferred $or ar.
The optionally substituted mononuclear or dinuclear
aromatic or araliphatic hydrocarbon radical represented by ar
in the amines o~ the iormula I I to be employed according to
the invention appropriately contains at least one sulpho group
or carboxyl group, but valuable dyestufts according to the
invention can also be obtained with radicals oi the general
deiinition o~ ar which contain no acid group conierring solu-
billty ln water. In addition, each nucleus oi ar can be
substituted by one substltuent oi the group -OH, alkoxy with
1-4 C atoms, -CN, -CF3 or -SO2R6 or by an additional -SO3H
group or by one or two ident~cal or diiierent substituents oi
the groups halogen,

5899
-S02-N \ or -COOH. If ar is derived from a phenylene
R2
radical, in addition to a -S03H group which may be present,
it can be substituted by one to three identical or different
alkyl radicals with 1-4 C atoms.
~- Amines of the formula II in which ar is phenylene or
phenylene which is substituted by one or two carboxyl groups
or by one or two sulpho groups, or a naphthylene radical which
is substituted by one or two sulpho groups or a stilbenyl radi-
cal which is substituted by two sulpho groups, and in particular
those in which ar is a radical of the formula
S0311 ~0 ~ SO
, ~ , ~ ~ ~ ~ 3
S03H
' ~0311 S0311
or
S03U 1103S
the position shown here corresponding to the position in the
general formula I, are particularly pre~erably employed.
i Amongst amines of the formula II which contain a
~ Rl .
S2 N \ group in ar, those in which Rl and Rl indepen-
R2
dently of one another denote hydrogen, an alkyl radical with
2 or 3 C atoms which is optionally substituted by OH, alkoxy

1~58~9
with 1-3 C atoms, -COOH or -S03H, methyl, carboxymethyl or
sulphomethyl and also tho~e ln which R2 and R2 independently
o~ one another denote an slkyl radical with 2 or 3 C atoms
which ls optionally substltuted by OH, alkoxy with 1-3 C atoms,
-COOH or -S03~ or an unsubstituted alkyl radical with 1-20 C
atoms, but ln particular hydrogen, methyl, carboxymethyl or
an alkyl radical with 2 or 3 C atoms which ls optionally sub-
- stituted by OH, are preferred.
Particularly pre$erred meanings ~ Rl and R2 are hydro-
gen, methyl or ~-hydroxyethyl. Slmilarly, hydrogen, methyl
and ~-hydroxyethyl are particularly prei'erred meanings of R
and R2 .
Amines o~ the iormula II which, except i'or carboxylic
acid and sulphonic acid radicals, carry no iurther substituents
in the divalent radical ar, are particularly preierred.
Further preferred groups oi amine~ oi' the general i'orm-
ula II to be employed accordlng to the invention are charac-
terised in that R3 denotes hydrogen, methyl, carboxymethyl,
sulphomethyl or an ethyl radical which is optionally sub-
stituted by Cl, OH, alkoxy with 1 or 2 C atoms, -COOH or
-S03H, in particular hydrogen or methyl.
Amongst the amines Or the iormula II which contain
!j a -S02-R6 group ln ar, tho~e in which R6 is methyl, ethyl,
phenyl or carboxymethyl are preierred.
Those amines oi the general formula II to be employed
12

1095899
according to the in~ention in whlch l is O, k is 2 or 3 and
m is l or 2 and the sum oi' k + m is 4, are psrticularly pre-
ierred.
The substituents lndicated in iormula II can be in ths
3-posltionsand/or 4-po~ltion~ oi the phthalocyanine. The
3-posltion o~ the -~ub~tituents indicated is preierred. In
the phthalocyanine, 3-po-aitions are the 3-posltion, 3'-
position, 3n-position and 3"'-position and 4-positions are
the 4-po~ition, 4'-position, 4"-position and 4"'-position.
In the case where l represents 0, the amines oi' the
general ~ormula II requlred for the manuiacture according to
the invention oi the dyestuiis Or the i'ormula I are obtained
by reacting phthalocyanine 3-dl-sulphochlorldes, 3-trl-
sulphochlorides, 4-dl-sulphochlorldes, 4-trl-~ulphochlorides
or, prei'erably, 3-tetra-sulphochlorides or 4-tetra-sulpho-
chlorides with amines oi' the general iormula X
HN-ar-NE~2 X
R3
wherein R3 and ar have the meaning~ indicated above. Mono-
acylated amines, for example acylated amine~ o~ the formula Xa
HN-ar-N-C-CH Xa
n 3
R3 0
can also be employed lnstead o~ amines oi the i'ormula X.
In this case, the condensation product ~ormed is subsequently
sapon$~ied with phthalocyanine sulphochloride.

1~95899
., ' ' .
- If 1 in formula I and IV represents the number 1,
,' 'phthalocyanine 3-sulphochloride or 4-sulphochloride is reac-
, ted, in any desired sequence, with an amine of the general
,, formula XI
l XI
~,,, HN ~
, ~
,; ,in which R1 and R2 have the meanings indicated above, and with
an amine o~ the formula X in order to obtain amines of the
formula II.
In addition, however, there is also the possibility
of using from the beginning a mixture of amines of the formulae
X and XI. The reaction of phthalocyanine sulphochloride with
the amines mentioned is carried out in a manner which is,in
itself known by adding the amines, either consecutively or as
a mixture, to a concentrated aqueous suspension of the sulpho-
chlorides in water or in a mixture of water and organic solvents
which are miscible with water. However, it can also be
carried out in organic solvents alone. The temperature of'
the reaction mixture is kept at 0 to 35C and the pH value, which
during the reaction continually shiftB to the acid range, is
kept between 4 and 10, preferably between 6 and 8, by the
gradual addition of alkali. Possible alkalis are,the cus-
tomary substances which have an alkaline action, such as
sodium hydroxide solution, sodium carbonate, potassium
carbonate and trisodium phosphate. Sodium hydroxide
solution is preferred. A tertiary amine, such as, for
example, pyridine, is advantageously added in catalytic amounts
- 14 -

,, '- l~g~
to accelerate the reaction. It is possible to further pro-
cess the amines of the formula II directly in the aqueous
solution in which they are obtained, but it is as a rule
advantageous to isolate thern in order to freethem from any
fraction of unreacted amine of the formula X and/or XI which
may stili be present.
The following may be mentioned as amines of the
formula XI which can be used for the manufacture of amines of
the formula II: ammonia, methylamine, dimethylamine, ethyl-
amine, diethylamine, ~-hydroxyethylamine, ~-methoxyethylamine,
bis-~-hydroxyethylamine, aminoacetic acid, taurine, N-methyl-
taurine, butylamine, capryl~mine, laurylamine, aniline, tolui-
dine, chloroaniline, aniline-o-, aniline-m- or aniline-p-
sulphonic acid, aniline-o-, aniline-m- or aniline-p-carboxylic
acid, N-methylaniline, N-ethylaniline-o-, N-ethylaniline-m- or
N-ethylaniline-p-sulphonic acid, aniline-~-methane-sulphonic
acid,benzylamine, N-~-hydroxyethyl-benzylamine, benzylamine-
sulphonic acid and ~-acetylaminoethylamine.
The ~ollowing may be mentioned as examples of amines
of the formula X which can also be employed in the form of the
monoacyl compound: p-phenylenediamine, N-methyl-p-phenylene-
diamine, N-carboxymethyl-p-phenylenediamine, m-phenylenediamine,
N-~-hydroxyethyl-m-phenylenediamine, 1,4-phenylenediamine-2-
3ulphonic acid, 1-amino-4-N-sulphomethylamino-phenylene-2-
sulphonic acid, 1,4-phenylenediamine-2,5- or -2,6-disulphonic
acid, l-amino-4-N-methylamino-phenylene-2,6-disulphonic acid,
1,~-phenylenediamine-4-sulphonic acid, 1,3-phenylenediamine-
4,6-disulphonic acid, 2,4-diamino-toluene-6- or -6-sulphonic

acid, 2,6-diamino-toluene-4-sulphonic acid, 2,5-diamino-1,3,5-
trimethylbenzene-4-sulphonic acid, 2,6-diamino-1,3-diethyl-
benzene-4-sulphonic acid, 2,4-diamino-1-chlorobenzene-6-
sulphonic acid, 2,4-diamino-1-tert.-butyl-benzene-6-sulphonic
acid, 2,4-diaminotoluene-5- or -6-sulphamide, 2,6-diamino-
toluene-4-ethanol or -diethanolsulphamide, 1,4-diaminophenylene-
2-dimethylsulphamide, 1,3-d:i1minophenylene-4-sulphanilide,
1,3-diaminophenylene-4-~-hydroxyethylsulphone, N-ethyl-p-
phenylenediamine, N-propyl-p-phenylenediamine, N-butyl-p-
phenylenediamine, N-pentyl-p-phenylenediamine, N-hexyl-p-
phenylenediamine, N-~-hydroxy-propyl-p-phenylenediamine, N-~-
carboxy -propyl-p-phenylenediamine, N-Y-chloro-butyl-p-
phenylenediamine, N-~-methoxy-butyl-p-phenylenediamine, N-~-
propoxy-butyl-p-phenylenediamine, N-~-acetylamino-ethyl-p-
phenylenediamine, N-~-butyrylamino-ethyl-p-phenylenediamine,
N-benzoylamino-ethyl-p-phenylenediamine, l-N-methyl-3-amino-
benzene-4-sulphonic acid, 1-N-butyl-4-amino-benzene-3-sulphonic
acid, 2,4-diamino-phenol-6-sulphonic acid, 2,4-diamino-1-
methoxybenzene-5-sulphonic acid, 1,5-diaminonaphthalene, 1,5-
diaminonaphthalene-3-sulphonic acid, 1,5-diaminonaphthalene-4-
sulphonic acid, 1,5-diaminonaphthalene-Z-sulphonic acid, 1,6-
diaminonaphthalene-4-sulphonic acid, 1,4-diaminonaphthalene-
2-sulphonic acid, 1,4-diaminonaphthalene-5-sulphonic acid, 1,4-
diaminonaphthalene-7-sulphonic acid, 1,8-diaminonaphthalene-4-
sulphonic acid, 2,6-diaminonaphthalene-8-sulphonic acid, 2,6-
diaminonaphthalene-4,8-disulphonic acid, 1,5-diaminonaphtha-
lene-~,7-disulphonic acid, 1,4-diaminonaphthalene-5-carboxylic
acîd, 1,4-diaminonaphthalene-2-carbo~ylic acid, 1,8-diamino-
- 16 -

~58~9
..
naphthalene-3-carboxylic acid, 4,4'-diaminodiphenyl, 2,2'-
dimethyl-4,4'-diaminodiphenyl, 3,3'-dichloro-4,4'-diaminodi-
phenyl, 4,4'-diaminodiphenyl-2,2'-disulphonic acid, 3,3'-
dimethoxy-4,4'-diaminodiphenyl, 1-amino-4-aminomethyl-benzene,
l-amino-4-aminomethyl-benzene-3-sulphonic acid, 1-amino-4-~-
aminoethyl-benzene-2-sulphonic acid, 1-amino-4-Y-aminopropyl-
benzene-3-sulphonic acid, 2-amino-5-aminomethyl-naphthalene-1-
sulphonic acid, 4,4'-diamino-diphenylmethane-2,2'-disulphonic
acid, 4,4'-diamino-diphenylethane-2,2'-disulphonic acid, 4,4'-
diamino-diphenylethane-mono-sulphamide, 4,4'-diamino-diphenyl-
eth~ne-disulphamide, 4,4'-diaminostilbene-2,2'-disulphonic
acid, 4,4'-diamino-diphenylmethane, 4,4'-diamino-diphenylethane-
di-~-hydroxyethylsulphamide, 4,4'-diamino-diphenylamine-3-
sulphonic acid, 3,4'-diamino-6-methoxy-diphenylamine-2'-
sulphonic acid, 3,4'-diamino-4-methyl-diphenylamine-2'-
sulphonic acid, ~,3'-diaminobenzophenone-~,5'-disulphonic acid,
3,4'-diaminobenzophenone-3'-sulphonic acid, 4,4'-diamino-
diphenylsulphone, 4,4'-dichloro-3,3'-diamino-diphenylsulphone,
3,3!-diamino-4-methyl-diphenylsulphone-5-sulphonic acid and
3,3'-diamino-diphenylsulphone-4,4'-disulphonic acid.
In the manufacture according to the invention of the
dyestuffs of the general formula I, an amine of the phthalo-
cyanine series of the general formula II, the free amino group
being bonded to an aromatic C atom of the radical ar
- 17 -

1~9~9
.
.~,', (S03H)k
Pc / (502-N ~ 1) II
:' (S02-1-ar-NH2)m
': . R3
; and wherein Pc, ar, Rl, R2, R3, k, 1 and m havethe meanings - .
indicated above, is initially diazotised and coupled with a
succinic acid derivative of the formula III
RS-OOC-C~2-CH-COOR4
CO-Z III
-wherein R4 and R5 have the meanings indicated above and Z
denotes hydrogen, an alkyl radical with 1-10 C atoms which is
optionally substituted by alkoxy with 1-4 C atoms or alkoxy-. .
carbonyl with 2-6 C atoms, a phenyl radical which is optionally
substituted by Cl, Br, alkyl or alkoxy with 1-4 C atoms or
alkoxycarbonyl with 2-6 C atoms, in an aqueous medium at a pH
: value between 3 and 8.
Preferred succinic acid derivat.ives of the formula III
' are those in which R4 denotes an alkyl radical with 2-6, pre-
ferably 2, C atoms which is substituted by Cl, OH or al~.oxy
with 1-4, preferably 1-2, C atoms or an unsubstituted alkyl
radical with 1-18, preferably 1-6, C atoms, R5 denotes an
ethyl radical which is substil,uted by ~1, OH or alkoxy with
1-2 C atoms or an unsubstituted alkyl radical with 1-18 C
- atoms and Z denotes hydrogen, alkyl with 1-3 C atoms, phenyl,
- 18 -

:~9S899
: . .
methylphenyl or alkoxycarb(,~!yL with 2 or 3 C atoms.
Succinic acid derivatives of the formula III in which
R4 and R5 are identical and denote methyl or ethyl and Z rep-
resents a methyl group, are particularly preferred.
The diazotisation of amines of the general formula II
is carried out in a manner which is in itself known in an
-aqueous acid medium by reacting them with nitrous acid or an
agent which releases nitrous acid. A salt of nitrous acid,
in particular an alkali metal salt, such as sodium or potas-
sium nitrite, is generally employed, in a mineral acid medium,
as an agent which releases nitrous acid. In a preferred
embodiment a solution of sodium nitrite is added in the molar
ratio 1 : m to the neutral aqueous solution of 1 mol of an
amine of the formula II and this mixture is then allowed to
run into at least 2.5 mols, preferably 3 mols, ~f dilute
approximately 5-15% strength hydrochloric acid per mol of amino
group present at temperatures between -5 and +25C, preferably
-2 to +5C, whilst stirring. The diazo suspension thus
obtained is then reacted with a succinic acid derivative of
the general formula III at a pH value between 3 and 8, pre-
ferably between 4.5 and 5.5, by, for example, adding the
succinic acid derivative to the acid suspension of the dia-
zonium compounds and then adjusting the pH value to the
desired value by adding alkali, for example sodium hydroxide,
sodium carbonate, sodium bicarbonate, sodium acetate,
potassium carbonate or sodium phosphate. After stirring
for 1-3 hours, the diazotised amine can no longer be detected
and the formation of the hydrazone is complete. It can be
-- 19 --

~,~g~
separated out from the solution by salting-out, that is to say
by adding a neutral water-soluble salt, such as, for example,
sodium or potassium chloride. However, separating out is
in no way necessary for the further processing of the hydra-
zones; on the contrary, it is appropriate and advantageous
to employ the reaction solutions obtained during the coupling
direct for the further processing.
The aqueous medium in which the coupling reaction of
diazotised amines of the rormula II with succinic acid deriva-
tives of the formula III is carried out can also contain
organic water-miscible solvents, in particular lower aliphatic
alcohols, such as, for example, methanol, ethanol or isopropa-
nol~ Similarly, known coupling accelerators, such as, for
example, urea or pyridine, can be present during the coup-
ling reaction.
The second reaction step of the manufacturing processes
according to the invention, that is to say the cyclisation of
the hydrazone IV to the pyrazolone V, is carried out extremely
easily by the alkaline treatment of the aqueous solution of
hydrazones of the formula IV at temperatures between O and
100C, preferably 15 to 30C, at a pH value between 8 and 14
with splitting off of the alcohol of the formula R50H. The
cyclisation can be coupled with a saponification of the group
-~OOR4 of the pyrazolone formed to the free carboxyl group.
For this it is only necessary to carry out the reaction near
the upper limit of the pH value range indicated, for example
at pH values of 10 to 14. The cyclisation is appropriately
carried out direct in the reaction solution, obtained during
- 20 -

lOgS899
coupling, of hydrazones of the formula ~V by increasing its
pH value to 10 to 14, room temperature genenally bein~ suf-
ficient. A diazo solution of an amine of the formula VI
~2N-B-~-A - VI
- ~7
is appropriately added to the solution, thus obtained, of the
pyrazolone V without isolating the pyrazolone and after cooling
to temperatures between -5 and +35C, preferably +5 to +20C,
and the mixture is subsequently stirred, if necessary with
cooling, at temperatures between -5 and +25C, preferably +5
to +15C, until the coupling reaction has ended. During the
course of the coupling reaction, which has gener~ly ende~ after
only a few minutes, the pH value is kept at values from 3 to
8, preferably 5 to 6, by the successive addition of a buffer
substance or an alkali,
In amines of the formula VI to be employed according
to the invention as diazo components, A denotes a fibre-
reactive radical, Fibre-reactive ra~licals A are to be
understood as those which contain a radical which can be split
off as an anion or as a neutral radi~ or con~n an æti~ed double
bond which is capable of addition reactions, and which are thus
able of reacting with the hydroxyl groups of celluiose when
the dyestuffs are applied to cellulose materials in the pre-
sence of acid-binding agents and/or under the action of heat,
or, when applied to high-molecular weight polyamide fibres,
such as wool, with the nucleophilic centres of these fibres

109SB~
with the formation of coval~nt bonds. Radicals which can
be split off by nucleophilic attack are those which, because
of their pcsition in the periodic system and/or because of a
positive charge centre, are strongly electron-attracting.
Acti~ated double bonds are, for example, those which are con-
jugated with a polar double bond, for example a carbonyl group,
A large number of fibre-reactive groupings of this type are
known from the literature.
As examples of known fibre-reactive radicals A, there
may be mentioned: radicals of a,~-unsaturated acids, such as
the radicals of acrylic acid, ~-chloroacrylic acid, a-bromo-
acrylic acid and propiolic acid, also the radicals of acids
which either contain a substituent which can be easily
replaced nucleophilically, such as, for example, a halogen
atom, or which gives radicals of a,~-unsaturated acids when
a neutral or anionic group is split off, or which contains a
vinyl~ulphone or ~-halogenoalkyl or ~-sulphatoalkylsulphone
group, such as the radicals of chloroacetic acid, ~-chloro-
propionic acid, ~-phenylsulpho~ylpropionic acid, ~-pyridinium-
propionic acid, ~-sulphatopropionic acid o~ ~-sulphatoe~hane-
sulphonic acid, ~ -chloroethylsulphonyl)-butyric acid or
4-~-chloroethylsulphonylbenzoic acid.
Radicals of heterocyclic carboxylic or sulphonic acids
which carry a substituent which is easily replaced during
the course of the application by the radical of cellulose or
by a nucleophilic group of the wool or the polyamide, such as,
for example, the radicals of 2,3-dichloroquinoxaline-5- or -6-
sulphonic acid, 2,3-dichloroquinoxaline-5- or -6-carboxylic
- 22 -

. ~
acid, 2,4-dichloroquinazoline-6- or -7-su~phonic acid, 2,4-
dichloroquinazoline-6-carboxylic acid, 1,4-dichlorophthalazine-
6-carboxylic acid and the corresponding dibromo, monohalogeno-
monomethyl-sulphonyl or monohalogeno-mono-ethylsulphonyl
derivatives, 3,6-dichloropyridazine-4-carboxylic acid or 2,4-
dichloro-, 2,4-dibromo- or 2,4-difluoro-pyrimidine-5- or -6-
carboxylic acid or the corresponding monohalogeno-monomethyl-
sulphonyl or monohalogeno-monoethylsulphonyl deriyatives, and
2-chlorobenzthiazole-carboxylic acid or 2-chlorobenzthiazole-
sulphonic acid.
Radicals of six-membered heterocyclic compounds contain-
ing 2 or 3 N atoms, such as s-triazin-2-yl and pyrimidin-2-yl
or s-triazin-4-yl and pyrimidin-4-yl radicals, which carry on
at least one of the remaining 2-positions, 4-positions or 6-
positions, at least one substituent which can be easily
nucleophilically replaced. Substituents on the hetero-
cyclic compound which can be easily nucle~philically replaced
which may be mentioned are, for example, halogen (Cl, Br or F),
tertiary and quaternary amine, including hydrazinium, sulphonyl,
in particular optionally substituted Cl-C5-alkylsulphonyl and
optionally substituted phenylsulphonyl, thiocyano, sulphinic
acid and sulphonic acid. In cases where the pyrimidine ring
or triazine ring only ~rriesone such labile substituent, this
ring can carry one non-labile substituent on the remaining
carbon atom or more non-labile substituents on remaining
carbon atoms. A non-labile substituent is to be understood
as a group which is bonded to a carbon atom of the triazine
or pyrimidine ring by a covalent bond, this covalent bond
- 23 -

il~9~
.
not being broken open under the conditions used in applying
the reactive dyestuff.
Examples of these non-labile substituents which may
be mentioned are the amino group and mono-substituted or
di-substituted amino groups and etheri~ied hydroxyl and mer-
capto groups.
- Substituted amino groups which can be non-labile sub-
stituents of the heterocyclic compoundsare, in particular,
monoalkylamino and dialkylamino groups with 1-4 C atomæ in
the optionally substituted alkyl radicals and phenyla~mino and
naphthylamino groups which are unsubstituted or contain one or
two groups, preferably sulphonic acid groups, but can also con-
tain other known substituents customary in dyestuff chemistry.
Amines which can be used as non-labile substituents
are, for example: ammonia, methylamine, dimethylamine,
ethylamine, pentylamine, hexylamine, diethylamine, n-propyl-
amine, i-propylamine, di-i-propylamine, ~-hydroxyethylamine,
Y-aminopropanol~ ~-ethoxyethylami~e, ~-propo~yethylamine, ~-
methoxyethylamine, bis-~-methoxyethylamine, bis-~-hydroxy-
ethylamine, ethylethanolamine, cycl~hexylamine, N-m~thylcyclo-
hexylamine, amino~cetic acid, ~-sulpha~~o-propylamine, 'aurine,
N-methyltaurine, n-butylamine, i-butylamine, dimethylamino-
propylamine, piperidine, morpholine, aniline, o-, m- or p-
toluidine, o-, m- or p-chloroaniline, aniline-o-, aniline-m-
or aniline-p-sulphonic acid, aniline-2,4- or aniline-2,5-
disulphonic acid, aniline-o-, aniline-m- or aniline-p-
carboxylic acid, 4-aminotoluene-2- or 4-aminotoluene-3-sulphonic
acid, N-methylaniline, N-ethylaniline-o-, N-ethylaniline-m- or
- 24 _

- -
N-ethylaniline-p-sulphonic acid, aniline-~-methane-sulphonic
acid, benzylamine, N-~-hydroxyethyl-benzylamine, benzylamine-
sulphonic acid and ~-acetylaminoethylamine.
Etherified hydroxyl and mercapto groups are, in par-
ticular, alkoxy and alkylthio groups wit~l up to 4 carbon atoms
which are optionally substituted in the al~yl radical, phen-
oxy and phenylthio groups which can preferably c~rry in the
phenyl radicals sulphonic acid substituents, but also other
known substituents cu~tomary in dyestuff chemistry; also
chlorine atoms and cyano, nitro and carboxyl groups in the 5-
position of a pyrimidinyl radical fall within the category of
non-labile substituents, as do one oi the two chlorin~ atoms
in the 2,~-dichloroquinoxaline, 2,4-dichloroquinazoline or
l,4-dichlorophthalazine radical.
Hydroxy or thio compounds which can be used to intro-
duce non-reactive substituents are, for example: methanol,
ethRnol, prop~nol, i-propanol, butanol, i-butanol, ethylene
glycol, ethylene glycol monomethyl ether, ethylene glycol
monoethyl ether, diethylene glycol monomethyl ether, phenol, -
alkylphenyl with l-9 C atoms in the alkyl chain, phenol-o-,
phenol-m- or phenol-p-sulphonic acid, methylmercaptan, ethyl-
mercaptan, thiophenol and ~-hydroxyethylmercaptan.
Amino groups which for their part additionally carry
a reactive radical are an importan1; group of non-labile,
substituted amino groups. If this additional reactive radi-
cal is designated A', this group of non-labile sub~tltuents
of the radical A has the general formula
Het-BR-Het'-A~
- 25 -

1~5899
wherein Het and Het' independently of one another are an oxy-
gen or sulphur atom, but preferably an optionally substituted
-NH group, the bridge member BR is a divalent aliphatic, aro-
matic or araliphatic radical and A' is one of the radicals
mentioned above for A, but which for its part contains no ~ur-
ther reactive group in a non-labile group which may be pre-
sent.
With regard to the preferred meaning of Het and Het'
mentioned, the grouping -Het-bridge member-Het' is preferably
derived from aliphatic or aromatic diamines. Suitable
aliphatic diamines contain alkyl chains with 2-6 C atoms or
cycloalkyl chains with 5 or 6 C atoms, it being possible for
two cycloalkyl chains also to be linked by the radical of a
hydrocarbon with 1-3 C atoms. Although the alkyl and cyclo-
alkyl radicals can be substituted, except ~or the two amino
groups they generally contain no further substituents. Alkyl
chains which are interrupted by a secondary or tertiary nitro-
gen atom and diamines in which one or both nitrogen atoms are
substituted by an additional alkyl group with 1-6 C atoms or
by a cycloalkyl group with 5 or 6 C atoms, in addition to being
substituted by the alkyl chain, are also suitable. Ethylene-
diamine is preferred. Further examples which may be men-
tioned are: 1,3-diaminopropane, 1,2-propylenediamine, 3-
methylamino-propylamine, bis-(3-aminopropyl)-methylamine,
dipropylenetriamine, 2-aminomethylcyclopentylamine, 3-amino-1-
cyclohexylaminopropane, 4,4'-diaminodicyclohexylmethane, 1,3-
bis-(ethylamino)-propane, 2,2-bis-(4-aminocyclohexyl)-propane,
1,4-diaminobutane and 1,6-diaminohexane.
- 26 -

1~915899
Suitable aromatic or araliphatic diamines contain as
the hydrocarbon radical radicals of optionally substituted
mononuclear or dinuclear aromatic compounds of the benzene,
alkylbenzene, naphthalene, alkylnaphthalene, biphenyl or
diphenyl series, such as, for example, the radical of benzene,
sulphobenzene, disulphobenzene, naphthalene, sulphonaphthalene,
disulphonaphthalene, dimethylbiphenyl, disulphobiphenyl,
diphenylmethane, diphenylethane, sulphodiphenylmethane, sulpho-
diphenylamine and sulphodiphenyl ether. The radical of
benzene and its monosulphonic acid and disulphonic acids, such as,
forexample, the 1,4-phenylene, 1,3-phenylene, 2-sulpho-1,4-
phenylene, 3-sulpho-1,4-phenylene, 4- or 5-sulpho-1,3-phenyl-
ene, 2,6-disulpho-1,4-phenylene, 2,5-disulp~o-1,4-phenylene
and 4,6-disulpho-1,3-phenylene radicals
The following list contains further radicals of mono-
nuclear or dinuclear aromatic compounds which may be used as
bridge members: 2-carboxy-1,4-phenyleney 3-carboxy-1,4-phenyl-
ene, 4-, 5- or 6-carboxy-1,3-phenylene, 2-carboxy-6-sulpho-1,4-
phenylene, 2,5-dicarboxy-1,4-phenylene, 4-sulpho-1,5-naphthyl-
ene, 4-sulpho-2,6-naphthylene, 2-carboxy-1,5-naphthylene,
l-sulpho-2,6-naphthylene, 4,8-disulpho-2,6-naphthylene and
3,7-disulpho-1,5-naphthylene.
Further bridge members which may be used are derived
from the following hydrocarbons, the positions indicated in
brac~ets after the names designating the positions of the
bonds to the radicals Het (first number) and Het' (second num-
ber): 2,2'-dimethyl-diphenyl (4,4'), 3,3'-dimethoxy-diphenyl
(4,4'), 2,2'-disulpho-biphenyl (4,4~), diphenyl-ethane (4,4~),

diphenyl-methane (4,4'), 2,2'-disulpho-di~henyl-methane (4,4'),
3,3'-disulpho-diphenyl-ethane (4,4'), 2,2'-disulpho-diphenyl
ether (4,4'), stilbene-2,2~-disulphonic acid (4,4'), methyl-
phenyl (4,~), 1-methyl-phenyl-3-sulphonic acid (4,~), 5-
methyl-naphthalene-l-sulphonic acid (2,~, diphenylamine
(494'~ 2-sulphodiphenylamine (4,4') and 6-methoxy-diphenylamine-
2'-sulphonic acid (3,4').
Preferred radicals A and A' are, in particular, radi-
cal~ of six-membered heterocyclic compolmds which are derived
from s-triazine.
B is, in particular, a radical of a mononuclear or
dinuclear aromatic or araliphatic hydrocarbon which is option-
ally substituted by one -S03H group and which can be sub-
stituted, in each nucleus, by alkoxy with 1-4 C atoms, -502R6
or an additional -S03H group, by one or two identical or dif-
ferent substituents of the groups halogen,
~Rl
-S02-~ or -COOH or by one to three identical or dif-
R"
ferent alkyl radicals with 1-4 C atoms, Rl denoting hydrogen,
methyl, carboxymethyl, sulphomethyl, an alkyl radical with 2-6
C atoms which is optionally substituted by Cl, Br, OH, alkoxy
with 1-6 C atoms, alkanoylamino with 1-~ C atoms, preferably
acetylamino, benzoylamino,alkanoyloxy with 1-6 C atoms, pre-
ferably acetyloxy, -COOH or -S03H, a phenalkyl or naphthalkyl
radical with 1-3 C atoms in the aliphatic chain, phenyl or
naphthyl, it being possible for the arorlatic nuclei to be sub-
stituted by Cl, Br, OH, alkyl and/or alkoxy with 1-6 C atoms,
- 28 -

1~9~8~9
alkanoylamino with 1-6 C atoms, -COOH or -SO~H, R2 being hydro-
gen, methyl, carboxymethyl, sulphomethyl, an alkyl radical
with 2-6 C atoms which is optionally substituted by Cl, Br,
CH, alkoxy with 1-6 C atoms, alkanoylamino ~ith 1-6 C atoms,
benzoylamino, alkanoyloxy with 1-6 C atoms, -COOH or -S03H or
an unsubstituted alkyl radical with 6-20 C atoms and R6 den-
oting methyl, carboxyoxymethyl, alkyl with 2 or 3 C atoms,
benzyl or phenyl, it being possible for the aromatic nuclei
to be monosubstituted or disubstituted by -COOH or -S03H.
Araliphatic radicals represented by B are always bonded
to the primary amino group with the aromatic nucleus and to the
- ~ A group withthe alkylene chain. Mononuclear aromatic or
araliphatic radicals which can be represented by B are the
optionally substituted radicals phenylene and monomethylene-
phenylene or polymethylene-phenylene of the general formula
(CH2)n~
in which n denotes an integer from 1 to 10.
Dinuclear aromatic or araliphatic radicals which can
be represented by B are the optionally substituted radicals
naphthylene, monomethylene-naphthylene or polymethylene-
naphthylene of the general formula
(CN2)n ~
in which n denotes an integer from 1 to 3, and the optionally
substituted radicals of the formul~
- 29 -

1~9S899
' ~3C1~2~ ~-CH2 C~2
C~-C~ ~ , ~ O ~ , ~ N
CO ~ and ~ S2
Examples of mononuclear or dinuclear aromatic or arali-
phatic hydrocarbon radicals which can be represented by B in
the dyestuffs which can be manufactured according to the inven-
tion are: 1,4-phenylene, 1,3-phenylene, 2-sulpho-1,4-phenyl-
ene, 3-sulpho-1,4-phenylene, 4- or 5-sulpho-1~3-phenylene,
2-carboxy-1,4-phenylene, 3-carboxy-1,4-phenylene, 4-, 5- or 6-
carboxy-1,3-phenylene, 2-carboxy-5-sulpho-1,4-phenylene, 2-
carboxy-6-sulpho-1,4-phenylene, 3-carboxy-6-sulpho-1,4-phenyl-
ene, 6-carboxy-4-sulpho-1,3-phenylene, 5-carboxy-3-sulpho-
1,3-phenylene, 2,5-dicarboxy-1,4-phenylene, 4,6-dicarboxy-
1,3-phenylene, 2-chloro-5-sulpho-1,4-phenylene, 2-chloro-6-
~ulpho-1,4-phenylene, 3-chloro-6-sulpho-1,4-phenylene, 6-
chloro-4-sulpho-1,3-phenylene, 2-chloro-'~-carboxy-1,4-phenyl-
ene, 2,6-disulpho-1,4-phenylene, 2,5-disulpho-1,4-phenylene,
4,6-disulpho-1,3-phenylene, 3-chloro-6-carboxy-1,4-phenylene,
6-chloro-4-carboxy-1,3-phenylene, 4-chloro-5-carboxy-1,3-phenyl-
ene, 2-methyl-5-carboxy-1,4-phenylene, 2-ethyl-6-carboxy- t
.
- :~0 -

1~9585~9
:-.' ,
1,4-phenylene, 3-ethyl-6-sulpho-1,4-phenylene, 6-ethyl-4-
carboxy-1,3-phenylene, 6-propyl-4-sulpho-1,3-phenylene, 5-
isopropyl-4-sulpho-1,3-phenylene, 5-isopropyl-6-carboxy-1,3-
phenylene, 4-n-butyl-6-sulpho-1,3-phenylene, 3-n-butyl-6-
sulpho-1,4-phenylene 4-tert.-butyl-6-sulpho-1,3-phenylene,
3-isobutyl-6-sulpho-1,4-phenylene, 2,5-diisopropyl-6-sulpho-
1,4-phenylene, 2,4-diethyl-5-carboxy-1,3-phenylene, 2,4,6-
trimethyl-5-sulpho-1,3-phenylene~ 2-cyano-1,4-phenylene, 4-
cyano-1,3-phenylene, 2-cyano-5-sulpho-1,4-phenylene, 2-
trifluoromethyl-1,4-phenylene, 2-methylsulphonyl-1,4-phenyl-
ene, 2-ethylsulphonyl-1,4-phenylene, 4-~-methoxy-ethylsulphonyl-
1,3-phenylene, 4-sulpho-1,5-naphthylene, 8-sulpho-1,5-naphthyl-
ene, 4-sulpho-2,6-naphthylene, 2-carboxy-1,4-naphthylene, 2-
carboxy-1,5-naphthylene, 5-carboxy-1,4-naphthylene, 3-carboxy-
1,8-naphthylene, 3-carboxy-1,5-naphthylene, 4-carboxy-2,6-naph-
~ thylene, 4-carboxy-2,7-naphthylene, 1-sulpho-2,6-naphthylene, 8-
7 sulpho-1,3-naphthylene, 4,8-disulpho-2,6-naphthylene, 3,7-di-
sulpho-1,5-naphthylene, 1-sulpho-4-chloro 2,6-naphthylene, 1-
i chloro-5-sulpho-2,6-naphthylene, 1-chloro-7-sulpho-2,6-naphthyl-
ene, 2-chloro-6-sulpho-1,4-naphthylene, 1-methyl-4-sulpho-
2,6-naphthylene and 2-methyl-7-sulpho-1,4-naphthylene
In each of these radicals the azo group is in the l-position
; of the phenyl nucleus or in the l-position or 2-position of
the naphthalene nucleus In the list which follows,
; examples of compounds from which further divalent radicals
which can be represented by B are derived are indicated
The positions of the two bonds with which the divalent radi-
cals are bonded on the one hand to the azo group (first

1~5899 `
, . ,
position given) and on the other hand to the group -N-A
R7
(second position given) of the dyestuffs which can be ma
factured according to the in~ention are indicated in the
second colllmn of the table.
Compound from which B is derived Position of
the bonds of
. . ._
Diphenyl 4,4'
2,2'-dimethyl-diphenyl 4,4'
3,3'-dimethoxy-diphenyl 4,4'
3,3'-dichloro-diphenyl 4,4'
3,3'-dimethyl-diphenyl 4,4'
2,2'-disulpho-diphenyl 4,4'
diphenyl-ethane 4,4'
diphenyl ether 4,4'
2,2'-disulpho-diphenyl-methane 4,4'
2,2'-disulpho-diphenyl-ethane 4,4'
3,3'-disulpho-diphenyl-ethane 4,4'
2,2'-disulpho-diphenyl ether 4,4'
2-sulphamide-diphenyl-ethane 4,4'
2,2'-disulphamido-diphenyl-ethane 4,4'
2,2'-di-~-hydroxyethylsulphamido-diphenyl-
ethane 4,4'
stilbene-2,2'-disulphonic acid 4,4'
methyl-phenyl 4,~
l-methyl-phenyl-3-sulphonic acid 4,~
l-ethyl-phenyl-2-sulphonic acid 4,~
l-propyl-phenyl-3-sulphonic acid 4,~ J

1~95899
Compound from which B is derived Position of
the bonds of
. _
5-methyl-naphthalene-1-sulphonic acid 1,~
6-methoxy-diphenylamine-2'-sulphonic acid 3~4~
; 4-methyl-diphenylamine-2'-sulphonic acid 3,4'
diphenylketone-5,5'-disulphonic acid 3,3'
diphenylketone-~'-sulphonic acid 3,4'
diphenylsulphone 4,4'
~4,4'-dichloro-diphenylsulphone 3,3'
: ~ 4,4'-disulpho-diphenylsulphone 3,3'
4-methyl-5-sulpho-diphenylsulphone 3,3'
The optionally substituted radicals phenylene, naphthyl-
ene,
-Cll2~ , -CH2-C~12~ -C~12 ~-- and ~-CHDC:H_~
are preferred for B in the dyestuffs which can be manufactured
: according to the invention.
The optionally substituted mononuclear or dinuclear
aromatic or araliphatic hydrocarbon radical represented by B
appropriately contains at least one sulpho group or carboxyl
groùp, but valuable dyestuffs can also be obtained with radi-
cals of the general definition of B which contain no acid
group conferring solubility in water.
- Dyestuffs which can be manufactured according to the
invention in which B is phenylene or phenylene which is

lV95~9
substituted by one or two carboxyl groups or by one or two
sulpho ~-roups or a naphthylene radical which is substituted
by one or two sulpho groups or a stilbenyl radical which is
substituted by two sulpho groups, and in particular
those ln whlch B ls a radlcal of the ~ormula
S~H S ~ COOH S ~H
~ ~ ~ S03H ~ ~
03H ~ H ~ H S03H S03H S\03H
~ f f ~ ~-C~-CH ~
S03H ~703H
the posltlon shown here corresponding to the position ln the
general ~ormula I, are partlcularly preierred.
R7 denotes, ln partlcular hydrogen, methyl, carboxy-
methyl, sulphomethyl or an alkyl radical wlth 2-4 C atoms
whlch ls optionally substltuted by Cl, Br, OH, alkoxy with
1-6 C atoms, alkanoylamino with 1-6 C atoma, benzoylamlno,
alkanoyloxy with 1-6 C atoms, -COOH or -S03~.
Divalent radicals B which carry no iurther substltuents,
except for carboxylic acld and sulphonlc acid radicals are par-
ticularly pre~erred.
Examples of amines oi the ~ormula VI are lndlcsted in
the followlng table:
H2N-B-N-A
R7
D

1~958~9
H2N-B-N- A X
!j; ~
2N~ N- -C -C H-CH2
~03S~H -C-CH2-CH2-C
~10 3 S~ H -C -C -C H2
~03S -C ~
3 C 1
~o35~Ei "~,~502CH3
a2N~N- ¦

1095~g
A X
1103S~I ~
~1 -C~ ,N~ C 1
~03S `N Cl
IIO S~C~3 O~`N~ 1
2N o~
2 ~_ N- 1~ C 1
B2N~ X I Cl
~2N~ S03~ ~N~X C 1
,. ~

1095899
H2N-B-N- ¦ A ~ X
iiO3~N- ~ Nr'~N~ X ~ 1
HO 5~LCli2-H- ~ X
H2N--~CH2-HN- N ~N
H2N~ ,~ N X
HO S~N_ N~N
HO S~N- ¦ ~ N ~1' X ¦ N112
HO S~ N_ ~ N j~, X
3.7 _

1095899
H2N - B - N - A X
,_ _ ... _ ~
Ho35~N ¦ ~, N~X ¦ 3
CH3
IX103~N303ll ~, N~ X -O-CN2-CN2_o CH3
2N~so3H _~Ny X
~03S~ N C 1 H2 2 H~N ~3 3
JIOSS~N ~ ~ -N~3Nl~N~ ~ COOH
liO3~U ~N"~ X 5033 ~
3 _~N ~, X 11~ ~ ~OC2H5
11 C l
-- 3~3 --
n~

~OgS899
~2N - B- N - A X
. ,
03S~ ~ rN'~;~X Cl
1103S ¦ ~X ¦ - ~3so33
~û3S~}l C ~ 'C l
32N~_N~ S02-C 33
~12N~N- ~30 -CH
'12 N~ N- C 1'~

1~95899
H2N-B-N- A X
R7
Ei2N~ N- N~, N - N~l~ ,~N ?' Z S
~03S ~; ¦ -N ~ CH-C~ ~ N ~1
Amlnes oi the ~ormula VI are manuiactured in a manner
which is in itsel~ known by acylating diamines oi the formula
VIII with acylating agent~ of the iormula XA according to the
reaction equation
2 ~ ~2N-B-N-A + HX
R7 R7
VIII VI
In thls equatlon X denotes a group which can split Orr by
the nucleophilic attack o~ the diamine.
Examples o~,diamines VIII whlch lead to amines of
the rormula VI by the reaction according to the above
equation are given by the i'ollowing list:
p-phenylenediamine, N-methyl-p-phenylenediamine,
N-carboxymethyl-p-phenylenediamine, m-phenylenediamine, N-~-

i~9s~99
hydroxyethyl-m-phenylenediamine, 1,4-phenylenediamine-2-
sulphonic acid, l-amino-4-N-sulphomethylamino-phenylene-2-
sulphonic acid, 1,4-phenylenediamine-2,5- or -2,6-disulphonic
acid, l-amino-4-N-methylamino-phenylene-2,6-disulphonic acid,
1,3-phenylenediamine-4-sulphonic acid, 1,3-phenylenediamine-
4,6-disulphonic acid, 2,4-diamino-toluene-5- or -6-sulphonic
acid, 2,6-diamino-toluene-4-sulphonic acid, 2,5-diamino-1,3,5-
trimethylbenzene-4-sulphonic acid, 2,6-diamino-1,3-diethyl-
benzene-4-sulphonic acid, 2,4-diamino-1-chlorobenzene-6-
sulphonic acid, 2,4-diamino-1-tert.-butyl-benzene-6-sulphonic
acid, 2,4-diaminotoluene-5- or -6-sulphamide, 2,6-diamino-
toluene-4-ethanol or diethanol-sulphamide, 1,4-diaminophenylene-
2-diethylsulphamide, 1,3-diaminophenylene-4-sulphanilide, 1,3-
diaminophenylene-4-~-hydroxyethylsulphone, N-ethyl-p-phenylene-
diamine, N-propyl-p-phenylenediamine, N-butyl-p-phenylenediamine,
N-pentyl-p-phenylenediamine, N-hexyl-p-phenylenediamine, N-~-
hydroxy-propyl-p-phenylenediamine, N-~-carboxy-propyl-p-
phenylenediamine, N-Y-chloro-butyl-p-phenylenediamine, N-~-
methoxy-butyl-p-phenylenediamine, N-~-propoxy-butyl-p-pheny-
lenediamine, N-~-acetylamino-ethyl-p-phenylenediamine, N-~-
butyrylamino-ethyl-p-phenylenediamine, N-benzoylamino-ethyl-
p-phenylenediamine, l-N-methyl-3-amino-benzene-4-sulphonic
acid, l-N-butyl-4-amino-benzene-3-sulphonic acid, 2,4-diamino-
phenol-6-sulphonic acid, 2,4-diamino-1-methoxybenzene-5-
sulphonic acid, 1,5-diaminonaphthalene, 1,5-diaminonaphthalene-
~-sulphonic acid, 1,5-diaminonaphthalene-4-sulphonic acid,
1,5-diaminonaphthalene-2-sulphonic acid, 1,6-diaminonaphthalene-
4-sulphonic acid, 1,4-diaminonaphthalene-2-sulphonic acid,
- 41 -

109~g9
l,4-diaminonaphthalene-5-sulphonic acid, l,4-diaminonaphthalene-
7-sulphonic acid, l,8-diaminonaphthalene-4-sulphonic acid,
æ6~n~nonaphthalene-8-sulphonic acid~ 2,6-diaminonaphthalene-
4,8-disulphonic acid, l,5-diclminonaphthalene-3,7-disulphonic
acid, l,4-diaminonaphthalene-5-carboxylic acid, l~4-diamin
naphthalene-2_carboxylic acid, l,8-diaminonaphthalene-3-
~ carboxylic acid, 4,4'-diaminodiphenyl, 2,2'-dimethyl-4,4'-
diaminodiphenyl, 3,3'-dichloro-4,4'-diaminodiphenyl, 4,4'-
diaminodiphenyl-2,2'-disulphonic acid, 3,3'-dimethoxy-4,4'-
diaminodiphenyl, l-amino-4-aminomethyl-benzene, l-amino-4-
aminomethyl-benzene-3-sulphonic acid, l-amino-4-~-aminoethyl-
benzene-2-sulphonic acid, l-amino-4-Y-aminopropyI-benzene-3-
sulphonic acid, 2-amino-5-aminomethyl-naphthalene~l-sulphonic
acid, 4,4'-diamino-diphenylmethane-2,2'-disulphonic acid, 4,4'-
diamino-diphenylethane-2,2'-disulphonic acid, 4,4'-diamino-
diphenylethane-mono-sulphamide, 4,4'-diamino-diphenylethane-
~ disulphamide, 4,4'-diaminostilbene-2,2'-disulphonic acid,
: 4,4'-diamin~-diphenylmethane, 4,4'-diamino-diphenylethane-di- ~-hydroxyethylsulphamide, 4,4'-diamino-diphenylamine-3-
~ulphonic acid, 3,4'-diamino-6-methoxy-diphenylamine-2'-
. sulphonic acid, 3,4'-diamino-4-methyl-diphenylamine-2'-~ul-
phonic acid, 3,3'-diaminobenzophenone-5,5'-disulphonic acid,
3,4'-diaminobenzophenone-3'-sulphonic acid, 4,4'-diamino-
diphenylsulphone, 4,4'-dichloro-3,3'-diamino-diphenylsulphone,
3,3'-diamino-4-methyl-diphenylsulphone-5-sulphonic acid and
3,3i-diamino-diphenylsulphone-4,4'-disulphonic acid.
A large number of examples of acylating agents of the
formula XA which can be reacted with diamines to give amines
- 42 -

i~9s899
of the formula VI according to the above equation are des-
cribed in the literature. The most important ones, representing
the entire class, are mentioned in the following list: cyanuric
chloride and cyanuric bromide, dihalogeno-mono-amino-triazines,
it being possible for the amino group as the non-reactivè
substituent to be substituted analogously to the equation des-
cribed above, such as 2,6-dichloro-4-amino-triazine, 2,6-
dichloro-4-methylamino-triazine, 2,6-dichloro-4-hydroXyethyl-
aminotriazine, 2,6-dichloro-4-phenylaminotriazine, 2,6-
dichloro-4-(o-, m- or p-sulphophenyl)-aminotriazine or 2,6-
dichloro-4-(2',4'- or 2',5'-disulphophenyl)-aminotriazine,
dihalogeno-alkoxy-sym.-triazines and dihalogeno-aryloxy-sym.-
triazine~, such as 2,6-dichloro-4-methoxytriazine, 2,6-
dichloro-4-i-propoxytriazine,or 2,6-dichloro-4-phenoxytriazine,
tetrahalogenopyrimidines, such as tetrachloro-, tetrabromo- or
tetrafluoro- pyrimidine, 2,4,5-trihalogeno-pyrimidines, such
a3 2,4,6-trichloropyrimidine, 2,4,6-tribromopyrimidine or
2,4,6-trifluoropyrimidine, 2,4,6-trichloro-5-nitropyrimidine,
2,4,6-trichloro-5-methylpyrimidine, 2,4,6-trichloro-5-carbo-
methoxypyrimidine or 2,4,6-trichloro-5-cyanopyrimidine or 2,6-
difluoro-4-methyl-5-chloropyrimidine, 2,4-difluoro-pyrimidine-
5-ethylsulphone, 2,6-difluoro-4-chloropyrimidine, 2,4,6-
tri~luoro-5-chloropyrimidine, 4,6-difluoro-2,5-dichloro-
pyrimidine or 4,6-difluoro-2,5-dibromopyrimidine, 2-methyl-
sulphonyl-4-chloro-6-methylpyrimidine, 2,6-bis-methylsulphonyl-
4,5-dichloropyrimidine, 2-methylsulphonyl-4,5-dichloro-6-
methylpyrimidine, 2-ethylsulphonyl-4,6-dichloropyrimidine,
derivatives of heterocyclic carboxylic or sulphonic acids,
- 43 -

1~95899
.
such as 3,6-dichloropyridazi.le-4-carboxylic acid chloride,
2y4-dichlor~pyrimidine-5-carboxylic acid chloride, 2,4,6-tri-
chloropyrimidine-5-carboxylic acid chloride, 2-methyl-4-
chloropyrimidine-5-carboxylic acid chloride, 2-chloro-4-
methylpyrimidine-5-carboxylic acid chloride, 2,6-dichloro-
pyrimidine-4-carboxylic acid chloride, 2-methylsulphonyl-6-
chloropyrimidine-4-carboxylic acid chloride or 2-methyl-
sulphonyl-6~chloropyrimidine-5-carboxylic acid chloride, 2-
ethylsulphonyl-6-chloropyrimidine-4-carboxylic acid chloride
or 2-ethylsulphonyl-6-chloropyrimidine-5-carboxylic acid chlor-
ide, 2,6-bis-(methylsulphonyl)-pyrimidine-4-carboxylic acid
chloride, 2-methylsulphonyl-6-methyl-4-chloropyrimidine-5-
` carboxylic acid chloride or bromide or 2-methylsulphonyl-6-
methyl-4-bromopyrimidine-5-carboxylic acid chloride or bro-
mide, 2,6-bis-(methylsulphonyl)-4-chloropyrimidine-5-carboxylic
acid chloride, 2- or 3-monochloroquinoxaline-6-carboxylic acid
chloride or 2- or 3-monochloroquinoxaline-6-sulphonic acid
chloride, 2- or 3-monobromoquinoxaline-6-carboxylic acid bro-
mide or 2- or 3-monobromoquinoxaline-6-sulphonic acid bromide,
2,3-dichloroquinoxaline-6-carboxylic acid chloride or 2,3-
dichloroquinoxaline-6-sulphonic acid chloride, 2,~-dibromo-
quinoxaline-6-carboxylic acid bromide o:r 2,3-dibromoquinoxa-
line-6-sulphonic acid bromide, 1,4-dichLorophthalazine-6-
carboxylic acid chloride or l,4-dichlorophthalazine-6-sulphonic
acid chloride and the corresponding bromine compounds, 2,4-
dichloroquinazoline-6-carboxylic acid chloride, 2,4-dichloro-
quinazoline-7-carboxylic acid chloride or 2,4-dichloro-
quinazoline-6-sulphonic acid chloride or 2,4-dichloro- !
- 44 -

1~9~8~9
.. .
.,
~uinazoline-7-sulphonic acid chloride and the corresponding
bromine compounds, N-methyl-N-(2,4-dichlorotriazinyl-6)-
aminoacetyl chloride, 2-chlorobenzthiazole-5-carboxylic acid
chloride or 2-chlorobenzthiazole-6-carboxylic acid chloride
or ~-chlorobenzthiazole-5-sulphonic acid chloride or 2-chloro-
benzthiazole-6-sulphonic acid chloride and the corresponding
bromine compounds, 2-methylsulphonyl- or 2-ethylsulphonyl- or
2-phenylsulphonyl-benzthiazole-5-sulphonic acid chloride or
2-methylsulphonyl- or 2-ethylsulphonyl- or 2-phenylæulphonyl-
benzthiazole-6-sulphonic acid chloride or aliphatic reactants,
such as acrylic acid chloride, mono-, di- or tri-chloro-
acrylic acid chloride, 3-chloropropionic acid chloride, 3-
ph~nylsulphonyl-propionic acid chloride, 3-methylsulphonyl-
propionic acid chloride, 3-ethylsulphonyl-propionic acid
chloride, 3-chloroethane-sulphochloride, ~-methylsulphonyl-
acrylic acid chloride and ~-bromoacrylic acid chloride.
The acylation of diamines of the formula VIII with the
compounds of the formula XA according to the above equation
is carried out in a manner which is in itself known in an
aqueous, aqueous-organic or organic solvent by means of a
Schotten-Baumann reaction at temperatures between 0 and 80C,
preferably between 10 and 25C, the acid liberated appro-
priately being neutralised or buffered off by adding al~ali,
such as, for example, sodium bicarbonate, sodium carbonate,
sodium hydroxide solution or sodium acetate. Possible org-
anic solvents are, above all, acetone, chlorinated hydrocarbons,
such as ethylene chloride or chlorobenzene, or also aprotic
polar solvents, such as dimethylformamide.
- 45 -

9~;899
The diazotisation of amines of the formula VI is
carried out in a manner which is in itself known in an aqueous
medium by reacting the amines with 1 m~l of nitrous acid, or
of an agent which releases nitrous acid, in the presence of
at least 2 equivalents, preferably approximately 2.5 equiva-
lents, of a strong acid, per 1 mol of amine A salt of
nitrous acid, in particular an alkali metal salt, such as
sodium or potassium nitrite, is generally employed, in a
mineral acid medium, as an agent which releases nitrous acid.
If the diazonium compound of an amine of the formula VI
is coupled to the pyrazolone V in the manufacturing process
according to the invention, che manufacture according to the
invention of water-soluble, fibre-reactive phthalocyanine azo
dyestuffs, has ended after the coupling reaction has ceased.
This embodiment of the process according to the invention is
preferred
The dyestuff can then be isolated from the aqueous solu-
tions thus obtained of the phthalocyanine azo dyestuffs by
salting-out, or it can be obtained in the form of a solid dye-
stuff preparation by ~pray-drying the solutions
In the manufacture according to the invention of the
dyestuffs it is also possib]e to couple diazonium compounds of
amines of the formula VII
H2N-B-E VII
wherein B has the meaning given above and E is a group which
an be converted to a group of the formula -N-A by known
R~
processes to the pyrazolone V~ Suitable groups for E are,
- 46 -

1095899
ior example, acylamlno groups o~ the i'ormula IX
N-acyl IX
R7
wherein acyl is any desired alipbatic or aromatic acyl group
which can be split oii' by saponii'ication. Aliphatic acyl
groups appropriately have no more than 3 C atoms, prei'erably
2 C atoms; aromatic acyl groups are appropriately derivatlves
oi the benzoyl group, pre~erably benzoyl itsel~.
I~ E represents an acylamino group oi' this type, the
dyestuii's are saponli'ied, approprlately by warmlng with
alkalis, such as, i'or example, 2-10~ strength sodium hydroxide
solutlon, to temperatures from 80 to 120C and the dyestui'i's
thus obtsined o~ the i'ormula Ia
(S03H)k
Pc (S2 N \ )
R2 1
\ H0 N~N - B-NH Ia
(S2-N ar-N ~ R7
R3 C\OOR4 m
wherein B, Pc, ar, Rl, R2, R3, R4, R7, k, l and m have the
meanings given above, are acylated with an acylating agent
o~ the formula X-A. The same reaction conditions and com-
pounds X-A which are in themselves known and which were indi-
cated ~bove ior the manufacture oi' amines of the ~ormula VI,
are suita~le ~or this.
47
n-

1~9S899
Furthermore, it is possible to employ amines of the
formula VII in which E denotes a nitro group in the manufac-
ture according to the invention oi dyestuifs in wbich R7 is
H. The phthalocyanine azo dyestuifs thus obtained are
reduced in a manner which is ln itself known and the dyestuffs
of the formula Ib then present
( S3H ) k
~ 1
PC . ( S02-N ,~
\ R2 1 Ib
\ N-N - B-NH2~
(S02-N--nr-N ~ ooR4 J m
wherein B, Pc, ar, Rl, R2, R3, R4, k, 1 and m have the meanings
given above, are then acylated in a manner which is in itseli
known with an acylating agent oi' the iormula XA, ~lbre-reactive
dyestufis oi the i'ormula I belng obtai~ed.
The water-soluble fibre-reactive phthalocyanine dye-
stufi's which can be manu~actured according to the invention are
outstandingly sultable i'or dyelng and prlnting cellulose mat-
erlals, cellulose-containing materials and natural and
synthetic polyamids materials. They are distingulshed by a
high degree oi ~ixing, in particular during printing
processes and fixing by dry heat, and good washing-out of
the non-~ixed portion o~ dyestuf~ and givc yel~owish-tinged
to bluish-tinged green dyeings and prlnts oi high brilliance
and depth oi colour with very good fastness to llght,
good fastness to wet ~
48
~,'

1~95899
.
processing, such as washing at 60C and 9~C, fastness to
sea water, fastness to acid and alkaline perspiration, fastness
to chlorinated water, fastness to peroxide and fastness to flue
gas.
Mixtures of dyestuffs which can be manufactured accord-
ing to the invention, in particular those in which the meanings
of k and/or 1 and/or m in the individual components are dif-
ferent, are outstandingly suitable for dyeing and printing
cellulose materials and have the same advantageous properties
as the individual dyestuffs. Mixtures of this type are
obtained, for example, if amines of the formula II having
individual components which are different to one another with
respect to the meanings of k and/or 1 and/or m are used as
starting materials in the manufacture, according to the inven-
tion, of mixtures. Mixtures of amines of the formula II
in which one component is generally substantially predominant,
are usually obtained when they are manufactured by reacting
phthalocyanine sulphochlorides with amines.
Example 1:
188 g of m-phenylenediamin~-su!phoaic acid are dis-
solved in about 6,000 ml of water -to give a neutral solution.
190 g of cyanuric chloride, dissolved in acetone, are added to
this solution at 0-5C and the pH is simultaneously kept bet-
ween 6 and 7 with about 100 ml of 10 N sodium hydroxide solu-
tion. When no further m-phenylenediamine-sulphonic acid
can be detected, 70 g of sodium nitrite are added to the
neutral solution and the mixture is then stirred into 250 ml
of 10 N hydrochloric acid at 0-3C When the diazotisation
- 49 -

5899
ceases, the diazo suspension is added to a solution of N-~3-
(3-carboxy-5-hydroxy-1-pyrazolyl)-4-sulpho-phenyl]-Ni-tri-
sulpho-phthalocyaninylsulphonamide, to which 100 g of bicar-
bonate have previously been added, The coupling ceases in
a few minutes,
The green phthalocyanine azo dyestuff formed can be
isolated by salting out or spray-drying,
The solution of the phthalocyaninepyrazolone,
required for the coupling reaction, can be obtained in the
following manner:
1,060 g of 3-(3-amino-4-sulpho-phenyl)-amino-sulphonyl-
nickel-phthalocyanine-3',3", 3"'-trisulphonic acld, manufac-
tured in the customary manner by condensation reaction of nickel
phthalocyanine sulphochloride with 1,3-diaminobenzene-4-sul-
phonic acid, are stirred with 7,000 ml of water and dissolved
by adding 400 ml of 10 N sodium hydroxide solution, 72 g
of sodium nitrite are added to this solution and the mixture
is then stirred into a mixture of 2,000 g of ice and 300 ml
of concentrated hydrochloric acid in the course of 30 minutes,
A temperature of 0 to 5C is maintained by adding a further
2,000 g of ice, After a short time, any possible excess
of nitrite is decomposed by adding aminosulphonic acid,
21 g of acetylsuccinic acid dimethyl ester are poured into
the diazo suspension thus obtained. The p~ value is sub-
sequently initially kept at 5,5 by sprinkling in approximately
13 g of sodium carbonate, and then at ~ to 6 with approximately
21 g of sodium bicarbonate. The mixture is subse-
quently stirred for approximately 1 hour. The end of the t
-- ~0 --

l~S899
reaction can be recognised as bein~ when the pH remains con-
stant and when no change in shade occurs if a solution of
H-acid in 2 N sodium carbonate is added to a sample.
~ 50 ml of 10 N hydroxide solution are added to the
solution thus obtained of 3-(nickel-trisulpho-phthalocyaninyl-
sulphonylamino) -6-sulpho-phenylhydrazone of oxalacetic acid
dimethyl ester, whereby the l-H ris~s to values of 12 to 13.
The mixture ~ stirred ~r several hours,preferablyovernight, at
room temperature. The rearrangem~nt to gi~e N-[3-(3-carboxy-5-
hydroxy-l-pyrazolyl)-4-sulpho-phenyl]-nickel-trisulpho-phthalo-
cyaninyl-sulphonamide is then complete; the pH is adjusted
back to 8 with a little hydrochloric acid and the resulting
crude solution is employed direct in the coupling reaction.
If the cyanuric chloride in the manufacture of the
diazo component is replaced by a molar amount of one of ~he
acylating agents in the following and the procedure followed
is otherwise as described above, valuable green reactive dye-
stuffs are likewise obtained: 2,4,6-trisulpho-1,~,5-triazine,
~-chloropropionic acid chloride, a,~-dibromopropionic acid
chloride, ~-phenylsulphonylpropionic acid chloride, ~-pyri-
diniumpropionic acid chloride, ~-sulphatopropionic acid
chloride, acrylic acid chloride, ~-bromoacry~c acid chloride,
3-~-chloroethylsulphonylbenzoic acid chloride, 4-vinylsul-
phonylcyclohexanecarboxylic acid chloride, 4-~-chlorbethyl-
sulphonyl-2,5-endomethylene-cyclohexanecarboxylic acid chloride,
w-(~-chloroethylsulphonyl)-butyric acid chloride, 2,4-dichloro-
pyrimidine-5-carboxylic acid chloride, 2,4-dibromo-pyrimidine-
5-carboxylic acid bromide, 2,4-difluoro-pyrimidine-5-carboxylic
-- ~1 --

l~9S899
acid chloride, 2,6-dichloro-pyrimidine-4-carboxylic acid
chloride, 2,3-dichloroquinoxaline-6-carboxylic acid chloride,
2,3-dichloroquinoxaline-6-s~lphonic acid chloride, 1,4-
dichloro-phthalazine-6-sulphonic acid chloride, 1,4-dichloro-
phthalazine-6-carboxylic acid chloride, 2-methylsulphonyl-6-
chloro-pyrimidine-4-carboxylic acid chloride, 3,6-dichloro-
pyridazine-4-carkoxylic acid chloride, 2-methylsulphonyl-6-
chloro-pyrimidine-5-carboxylic acid chlorideand 2,6-bis-
(methylsulphonyl)-pyrimidine-~-carboxylic acid chloride.
If the condensation product of nickel phthalocyanine
sulphochloride and one of the amines mentioned in the following
is used in the manufacture of the coupling component instead
of the condensation product mentioned above of nickel phthalo-
cyanine sulphochloride and 1,3-diaminobenzene-sulphonic acid
and the procedure followed is otherwise as described, vaIuable
green reactive dyestuffs are likewise obtained: 1,4-phenylene-
diamine-2-sulphonic acid, 1,3-phenylenediamine-4,6-disulphonic
acid, 1,4-phenylenediamine-2,5-disulphonic acid, 1,4-phenylene-
diamine-2,6-disulphonic acid, 2,4-diaminotoluene-6-sulphonic
acid, 2,6-diaminotoluene-4-sulphonic acid, 2,4-diamino-1,3,5-
trimethylbenzene-6-sulphonic acid, 2,6-diaminonaphthalene-4,8-
disulphonic acid, l,~-diaminonaphthalene-2-sulphonic acid,
2,6-diaminonaphthalene-8-sulphonic acid, 1-amino-4-amino-
methyl-benzene-3-sulphonic acid, 2-amino-~-aminomethyl-naphtha-
lene-l-sulphonic acid, 4,4'diamino-diphenylamine-3-sulphonic
acid, 3,~'-diamino-4-methyl-diphenylsulphone-~-sulphonic acid,
1,3-phenylenediamine (acetyl derivative, subsequently saponi-
fied), 2,4-diaminotoluene (acetyl derivative, subsequently
- ~2 -

l/D~S899
saponified), 1,4-phenylenediamine (acetyl derivative, subse-
quently saponified), 4,41-diamino-diphenylethane-2-2'-disul-
phonic acid, 4,4'-diamino-diphenylethane-mono-sulphamide,
4,4'-diamino-diphenylethane-disulphamide, 4,4'-diaminostilbene-
2-2'-disulphonic acid, 4,4'-diamino-diphenylethane-di-~-
hydroxyethylsulphamide, 4,4'-diamino-diphenylamine-3-sulphonic
acid, 3,4'-diamino-6-methoxy-diphenylamine-2'-sulphonic acid,
3-4'-diamino-4-methyl-diphenylamine-2'-sulphonic acid, 3,3'-
diaminobenzophenone-5-5'-disulphonic acid, 3,4'-diaminobenzo-
phenone-3'-sulphonic acid, 4,4'-diamino-diphenylsulphone,
4,4'-dichloro-3-3'-diamino-diphenylsulphone, 3,3'-diamino-4-
methyl-diphenylsulphone-5-sulphonic acid and 3,3'-diamino- -
diphenylsulphonic-4-4'-disulphonic acid
Exam~le 2:
268 g of p-phenylenediamine-2,6-disulphonic acid are
reacted in the customary manner with 1~3 g of methoxy-dichloro--
triazine. After adding 70 g of sodium nitrite, the solution
of the resulting condensation product is allowed to run into
250 ml of 10 N hydrochloric acid, and the diazo suspension
thus obtained is subsequently added, we described in Example
15 to a solution of bispyrazolone manufactured as described
below from 535 g of 3,3'-bis-~(4-aminophenyl)-aminosulphonyl]-
nickel-phthalocyanine-3",3"'-disulphonic acid. The pH is
subsequently adjusted to 7 - 7.2 with 4 N sodium carbonate
solution and the green dyestuff formed is isolated by salting
out or spray-drying
The bispyrazolone employed as the coupling component
was manufactured in the following mar~er:
- ~3 -

~9
535 g of 3,3'-bis~4-aminophenyl)-amino-sulphonyl~-
nickel-phthalocyanine-3",3"~-disulphonic acid, manufactured in
the customary manner by condensation of 0.5 mol of nickel
phthalocyanine tetrasulphochloride with l mol of acetyl-p-
phenylenediamine and saponification of the condensation pro-
duct, are stirred with 3,500 ml of water and dissolved by
adding 200 ml of 10 N sodium hydroxide solution. 70 g of
sodium nitrite are added to this solution and the mixture is
then stirred into a mixture of 2,000 g of ice and 300 ml of
concentrated hydrochloric acid in the course of about 30
minutes. The temperature is kept between 0 and 5C by
adding a further lO0 g of ice. The mixture is subsequently
stirred for about lO minutes and any possible slight excess of
nitrite is then removed with aminosulphonic acid 135 g
of acetylsuccinic acid diethyl ester are added to the diazo
suspension thus obtained The pH is adjusted to about 6
with approximately 250 g of sodium carbonate and kept at this
value until no further diazo compound can be detected A
solution of turquoise-coloured 3,3'-bis-[4-(1,2-bis-ethoxy-
carbonyl-ethylidene)-hydrazino-phenyl-amino-sulphonyl-]nickel-
phthalocyanine-3",3"'-disulphonic acid is thus obtained, which
is converted direct to the corresponding bispyrazolone by
the action of alkali by adding about 400 ml of 10 N sodium
hydroxide solution and stirring the mixture at room temperature
for approximately 4 hours.
If the corresponding 4,4',4",4"'-derivative is used
instead of the amine employed above, vaLuable phthalocyanine
hydrazones are likewise obtained~
- ~4 -

~95899
If the condensation product of nickel phthalocyanine
sulphochloride and two mols of one of the amines mentioned
in the table which follows is used as the diazo component for
the pyrazolone step instead of the amine employed above and
the procedure followed is otherwise as described above, ~reen
phthalocyanine azo dyestuffs are likewise obtained. 1,3-
phenylenediamine (acetyl derivative, subsequently saponified),
2,4-diaminotoluene (acetyl derivative, subsequently saponi-
fied), 2,4-diaminoanisole (acetyl derivative, subsequently
saponified), 1,4-phenylenediamine-2-sulphonic acid, 2,4-diamino-
toluene-6-sulphonic acid, 4-amino-benzylamine (4-acetyl deriva-
tive, subsequently saponified), 4,4'-diaminostilbenedisul-
phonic acid, 4,4'-diaminomethanedisulphonic acid or 4,4'-
diamino-diphenylamine-3-sulphonic acid.
If the acetylsuccinic acid diethyl ester employed as
the coupling component for the pyrazolone step is replaced by
one of the following derivatives of succinic acid, arylhydra-
zones which can be processed according to the invention togive
valuable azo phthalocyanine dyestuffs are likewise obtained.
R~ - OOC - CH2 - CH - COO - R4
C - Z
, O
R5 R4 Z
.. . . ..
-CH3 -CH3 -H
-CH3 -C2H4C1 -CH3
-CH3 -i-C3H4 -CH3
-CH3 -i-C4H9 -COO-CH3
-
- 55 -

l~S~
R5 R4 Z
-CH3 -i-C6Hll -COO-C2H5
-CH3 C2H4 OH . -CH3
-CH3 -C3H6-OCH3 -COO-C3H4
-CH3 . C2H5 -COO-C3H4
-C3H7 C2H5 -C3H7
C5Hll -C2H5 -CH2-C6H5
gHlg -C2H5 -COO-CH3
-C16H33 -C2H5 -C6H5
-C2H4-O-C2H5 -C2H5 C6H4 CH3
If methoxydichlorotriazine is replaced by one of the
reactive components mentioned in the following during the
acylation of p-phenylenediamine-2,6-disulphonic acid, soluble
dyestuffs are likewise obtained. 2-amino-4,6-dichloro-
1,3,5-tria~ne, 2-phenoxy-4,6-dichloro-l,3,5-triazine, 2-
phanylamino-4,6-dichloro-l,3,5-triazine, 2-N-methyl-N-phenyl-
amino~4,6-dichloro-l,3,5-triazine, 2-buty:lmercapto-4,6-di-
chloro-l,3,5-triazine, 2-~-methoxyethoxy-4,6-dichloro-l,3,5-
triazine, 2-(2'-carboxyphenoxy)-4,6-dichloro-l,3,5-triazine,
2-carboxymethylthio-4,6-dichloro-l,3,5-triazine, 2-phenylthio-
4,6-dichloro-1,3,5-triazine, condensation product of l mol of
cyanuric chlo~ide and l mol of 2-~-amino-ethylamino-4-~2',5'-
disulphophenylamino~-6-chlorotriazine-l,3,5, condensation
product of cyanuric chloride and l mol of 2-4'-amino-3'-
sulpho-phenylamino-4-(2"-carboxyphenylamino)-6-chlorotriazine-
l,3,5, condensation product of cyanuric chlorlde and l mol of
2-3'-amino-4'-sulpho-phenylamino-4-n-butoxy-6-chlorotriazine-
- ~6 -

lO9S~
.
1,3,5,12,4-disulpho-6-chloro-1,3,5-triazine, tetrachloro-
pyrimidine, 2,4,6-trichloropyrimidine, 5-cyano-2,4,6-tri-
chloropyrimidine, 5-nitro-2,4,6-trichloropyrimidine, 2,4-
difluoro-6-chloropyrimidine, 2-methylsulphonyl-4-methyl-6-
chloropyrimidine,,condensation product of cyanuric chloride
and 2-methoxy-4-~-hydroxyethoxy-6-chloro-1,3,5-triazine, 2-
methylsulphonyl-4,6-dichloropyrimidine, 2,3-dichloroquinoxyline-
5-carboxylic acid chloride, 2,3-dichloroquinoxyline-6-carboxy-
; lic acid chloride, 2,3-dichloroquinoxaline-5-sulphonic acid
chloride, 2,3-dichloroquinoxaline-6-sulphonic acid chloride,
¦2,4-dichloroquinazoline-6-carboxylic acid chloride, 2,4-
dichloroquinazoline-6-sulphonic acid chloride, 2,4-dichloro-
quinazoline-7-sulphonic acid chloride, 1,4-dichlorophthalazine-
6-carboxylic acid chloride, 3,6-dichloropyridazine-4-carboxy-
lic acid chloride, 2,4-dichoropyrimidine-5-carboxylic acid
chloride or 2,4-difluoropyrimidine-6-carboxylic acid chloride.
Exam~le 3:
If the correspondin~ molar amount of one of the amines
mentioned in the ta~le which follows is used instead of the
amine indicated in Example 1, that is to say 3-[(3-amino-4-
sulpho-phenyl)-amino-sulphonyl-]-nich~-phthalocyanine-3',3",3~"-
trisulphonic acid, and the procedure followed is otherwise
as indicated therein, valuable hydrazones of oxalacetic acid
methyl ester which can be further processed to correspondingly
substituted pyrazolones
- 57 -

~095899
/ ~03H)k R
Pc ( S02-N
,,, \ R2 /1
( S02-N-ar-NH2 )m
R3
sre likewise obtained.
58

l~g58~9
e
--1 ~-- - - .
c~
m~
~o~
m m
_ m ~ m ~ m
~ 0~ ~,
~ ~& ~ :1 m~ ~ m
3 m
~ 9

~95~99
E ~
. ~
_ ~
-t w I ~ ~ J iJ
n c
5C~
c~ c~=o
~Stq O ~. ~
m~ ~0 m
_ m
.
m
C~
o
m
~ U~ D =o, W.~ W~
m m m m~
-- 60 --

1~9S899
~, .
.. . . _ . _ .
_ _ _ _ _
,
:D m ~ m~
m
~, ~
' ~ j C~ '
; I ~ mc
m m
t
, I
u~ mN mN m~
~ . _ . .
~r4
m m m
-- 61 --

1~958~f9
E _1 ,. .. .. .. .. . ,.
i---- C`l N C`~
- ._
.' I ' .
~ ~ ~3 " m O
1' i o o
; 1 X
. ~ ~ I I . .
n o c~
q ~ ml m
. .. , .. ~
U C~ ~N N
._ . .. _ .. _.
5~ o
. ~ ~ O
. N C~l N r N N N
-- 62 --

1~5899
C~
~ ~ o o
,4 ~ ~ ~1 -~ O ~1
r; - m
o~
_ _
. . ..
tl
. pu~
~: m m m m c~
... _ ... . .
~:~
o o
~ ~ ~r
C~ C'`J N C~
U ~)
I I ~ I .
_ _ _ _ _ _ . . _
~ :~
P: O
;,: :~ m
-- 63 --

J' ~95~99
:
E c~l ~ ~
.,-
': ~4 ~1 0 0
6 ,~ r~ O
~ 1
",
','
m :c"'
0~
.,~
f
~S:
~.
.
~ 8
Y
:~
,'
~s
64
, ' ,.,~
~,

10958~9
Example 4:
If an at least molar amount of one of the compounds,mentioned in the following, which contain an amino group which
can be acylated is added to the dyestù~f manufactured according
to Example 1 and the mixture is then warmed, in each case for
one hour, to 30, 40 and 50, the pH being kept between 4
and 7 by adding alkali, such as sodium bicarbonate, sodium
carbonate or sodium hydroxide solution, valuable green reac-
tive dyestuffs are likewise obtained In the case of
ammonia or aliphatic amines, t.he alkali can be replaced by a
second mol of amine Ammonia, methylamine 9 diethylamine, iso-
propylamine, ethanolamine, diethanolamine, N,N-dimethylhydra-
zine, aniline, o-, m- or p-toluidine, N-methylaniline,
aniline-2-, aniline-3- or aniline-4-sulphonic acid, 2-, 3- or
4-aminobenzoic acid, aniline-methanesulphonic acid, ~-amino-
ethanesulphonic acid, N-methyltauriner aminoacetic acid,
aniline-2,4- or aniline-2,5-disulphonic acid or the condensa-
tion product of: p-phenylenediamine, cyanuric chloride and
aniline-3-sulphonic acid, ethylenediamine, cyanuric chloride
and aniline-2,4-disulphonic acid, 1,4-phenylenediamine-2,5-
disulphonic acid and iso-propoxy-dichlorotriazine, 1-3-phenyl-
enediamine-4-sulphonic acid and ~-ethoxyethoxydichlorotriazine,
p-phenylenediaminesulphonic acid and cyanuric chloride, p-
phenylenediam~esulphOniC acid and tetrachloropyrimidine, p-
phenylenediaminesulphonic acid and 2,3-dichloroquinoxaline-
carboxylic acid chloride, p-phenylenediaminesulphonic acid and
2,6-dichloropyrimidine-4-carboxylic acid chloride or p-phenyl-
enediaminesulphonic acid and ~,6-dichloropyridazine-4-carboxylic
- 65 -

- 1~)95899
''
; acid chloride.
Example 5:
The diazo component employed in Example 1, that is to
`~ say 2-amino-4-dichlorotriazinylamino-benzenesulphonic acid,
is replaced by an equivalent amount of 2-amino-4-acetylamino-
benzenesulphonic acid and the procedure followed is otherwise
.s
as described in Example 1.
200 ml of 10 N sodium hydroxide solution are subse-
quently added to the solution of the green azo phthalocyanine
dyestuff formed and the mixture is stirred for five hours at
95 until the acetyl group is completely saponified.
The dyestuff solution thus obtained is neutralissd
with about 100 ml of 10 N hydrochloric acid and a solution of
190 g of cyanuric chloride in acetone is then added at 0-5C.
The pH value is simultaneously kept between 5.0 and 6.5 by
adding about 80 g of sodium bicarbonate in portions. The
reaction has ended when no further amino groups which can be
diazotised can be detected.
The dyestuff thus obtained is identical to that manu-
factured according to Example 1.
'
- 66 -