FIBRE-REACTIVE AZO DYESTUFFS, THEIR MANUFACTURE AND USE

OBTENTION INDUSTRIELLE ET EMPLOI DE COLORANTS AZOIQUES REAGISSANT AVEC LES FIBRES

English Abstract

Abstract of the Disclosure
A fibre-reactive azo dyestuff of the formula
<IMG> (1)
in which A is a benzene or naphthalene radical, X is alkyl or
alkoxy with 1 to 4 carbon atoms, carboxyl or halogen, m is 1
or 2, n is 0 or 1 and p is 0 or 1, it being possible for A and
the benzene radical B to contain further substituents.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A fibre-reactive azo dyestuff of the formula
<IMG> (1)
in which A is a benzene or naphthalene radical, X is alkyl or alkoxy with
1 to 4 carbon atoms, carboxyl or halogen, m is 1 or 2, n is 0 or 1 and p is
0 or 1, it being possible for A and the benzene radical B to contain as
further substituents sulfo, alkyl groups with 1 to 4 carbon atoms, alkoxy
groups with 1 to 4 carbon atoms, acylamino groups with 1 to 6 carbon atoms,
amino groups, ureido, nitro, methylsulfonyl, hydroxy, carboxy and halogen,
and A is also sulfophenylazo; and the metal complexes of the fibre-reactive
azo dyestuffs of the formula (I).
2. A fibre-reactive azo dyestuff according to claim 1, in which A, B,
m, n and phave the meanings indicated in claim 1 and X is methyl, methoxy,
carboxyl or chlorine.
3. A fibre-reactive azo dyestuff according to claim 1, in which A is a
mono- or di-sulphobenzene radical, m is 1 or 2, n = 0 and X is methyl, methoxy,
carboxyl or chlorine.
4. A fibre-reactive azo dyestuff according to claim 1, in which A is
a mono- or di-sulphobenzene radical or a carboxybenzene radical, m = 2,
n = 1, p = 1 and X is methyl, methoxy, carboxyl or chlorine.

5. A fibre-reactive azo dyestuff according to claim 1, in which A
is a di- or tri-sulphonaphthalene radical, m = 1, n = 0 and X is methyl,
methoxy, carboxyl or chlorine.
6. A fibre-reactive azo dyestuff according to claim 1, in which A
is a di- or tri-sulphonaphthalene radical, m = 2, n =
26

1, p = 1 and X is methyl, methoxy, carboxyl or chlorine.
7. A copper complex compound of a fibre-reactive azo
dyestuff according to Claim 1, in which A is an ortho-hydroxy-
mono- or -di-sulphobenzene radical, m = 1, n = 1, p = 0 and X
is methyl, methoxy, carboxyl or chlorine.
8. A copper complex compound of a fibre-reactive azo
dyestuff according to Claim 1, in which A is an ortho-hydroxy-
disulphobenzene radical, m = 1, n = 0 and X is methyl, methoxy,
carboxyl or chlorine.
9. A copper complex compound of a fibre-reactive azo
dyestuff according to Claim 1, in which A is an ortho-hydroxy-
disulphophenylazobenzene radical, m = 1, n = 0 and X is methyl,
methoxy, carboxyl or chlorine.
10. A copper complex compound of a fibre-reactive azo
dyestuff according to Claim 1, in which A is an ortho-hydroxy-
disulphonaphthalene radical, m = 2, n = 0 and X is methyl,
methoxy, carboxyl or chlorine.
11. A fibre-reactive azo dyestuff according to Claim 4, in
which A is sulphophenyl, m = 2, n = 1, p = 1 and X is methyl,
methoxy, carboxyl or chlorine.
12. A fibre-reactive azo dyestuff according to Claim 5, in
which A is di- or tri-sulphonaphthyl-2, m = 1, n = 0 and X is
methyl, methoxy, carboxyl or chlorine.
13. A fibre-reactive azo dyestuff according to Claim 6, in
which A is disulphonaphthyl-2, m = 2, n = 1, p = 1 and X is
methyl, methoxy, carboxyl or chlorine.
14. A copper complex compound of a fibre-reactive azo dye-
27

stuff according to Claim 10,in which A is ortho-hydroxy-
disulphonaphthyl-2, m = 2, n = 0 and X is methyl, methoxy,
carboxyl or chlorine.
15. The fibre-reactive azo dyestuff according to Claim 12,
of the formula
<IMG>
16. The fibre-reactive azo dyestuff according to Claim 13,
of the formula
<IMG>
17. The copper complex compound of the fibre-reactive azo
dyestuff according to Claim l4, of the formula
<IMG>
18. Process for the manufacture of a fibre-reactive azo
dyestuff of the formula
28

<IMG> (1)
in which A is a benzene or naphthalene radical X is alkyl or alkoxy with
1 to 4 carbon atoms, carboxyl or halogen, m is 1 or 2, n is 0 or 1 and
p is 0 or 1, it being possible for A and the benzene radical B to contain
as further substituents sulfo, alkyl groups with 1 to 4 carbon atoms, alkoxy
groups with 1 to 4 carbon atoms, acylamino groups with 1 to 6 carbon atoms,
amino groups, ureido, nitro, methylsulfonyl, hydroxy, carboxy and halogen,
and A also sulfophenylazo; and the metal complexes of the fibre-reactive
azo dyestuffs of the formula (1), wherein a diazotised amino compound of the
formula
A-NH2 (2)
a coupling component of the formula
<IMG> (3)
2,4,6-trifluoro-1,3,5-triazine of the formula
<IMG> (4)
29

and an aminobenzene of the formula
<IMG> (5)
are reacted, by coupling and condensation, in any desired sequence to give
a fibre-reactive azo dyestuff of the formula(1) and optionally treating the
azo compound which, in the benzene or naphthalene radical A in the ortho-
position to the azo group, contains a complex-forming group, before or
optionally after the acylation with the fluoro triazine, with an agent which
donates a metal.
19. Process according to claim 18, wherein an aminobenzene of the
formula (5) in which X is methyl, methoxy, carboxyl or chlorine is used as
the starting material.
20. Process according to claim 18, wherein a diazotised amino compound
of the formula (2) is coupled with a coupling component of the formula (3)
to give an azo compound of the formula
<IMG> (6)
this is subjected to a condensation reaction with 2,4,6-trifluoro-1,3,5-
triazine of the formula (4) and the primary condensation product obtained
is subjected to a condensation reaction with an aminobenzene of the formula
(5) to give a fibre-reactive azo dyestuff of the formula (1).
21. Process according to claim 18, wherein a coupling component of
the formula (3) is subjected to a condensation reaction with 2,4,6-trifluoro-

1,3,5-triazine of the formula (4), the resulting primary
condensation product is subjected to a condensation reaction
with an aminobenzene of the formula (5) and the secondary
condensation product formed is coupled with a diazotised
amino compound of the formula (2) to give a fibre-reactive
azo dyestuff of the formula (1).
22. Process according to Claim 18, wherein a coupling
component of the formula (3) is subjected to a condensation
reaction with 2,4,6-trifluoro 1,3,5-triazine of the formu1a (4),
a diazotised amino compound of the formula (2) is coupled to
the resulting primary condensation product and the resulting
azo compound is subjected to a condensation reaction with an
aminobenzene of the formula (5) to give a fibre-reactive azo
dyestuff of the formula (1).
23. Process according to Claim 18, wherein a diazotised
amino compound of the formula (2), a coupling component of
the formula (3) and an aminobenzene of the formula (5), in
which A is a mono- or di-sulphobenæene radical, m is 1 or 2,
n = 0 and X is methyl, methoxy, carboxyl or chlorine, are
used as the starting materials.
24. Process according to Claim 18, wherein a diazotised
amino compound of the formula (2), a coupling component of
the formula (3) and an aminobenzene of the formula (5), in
which A is a mono- or di-sulphobenzene radical or a carboxy-
benzene radical, m = 2, n = 1, p = 1 and X is methyl, methoxy,
carboxyl or chlorine, are used as the starting materials.
31

25. Process according to Claim 18, wherein a diazotised
amino compound of the formula (2), a coupling component of the
formula (3) and an aminobenzene of the formula (5), in which
A is a di- or tri-sulphonaphthalene radical, m = 1, n = 0 and
X is methyl, methoxy, carboxyl or chlorine, are used as the
starting materials.
26. Process according to Claim 18, wherein a diazotised
amino compound of the formula (2), a coupling component of the
formula (3) and an aminobenzene of the formula (5), in which
A is a di- or tri-sulphonaphthalene radical, m = 2, n = 1,
p = 1 and X is methyl, methoxy, carboxyl or chlorine, are
used as the starting materials.
27. Process according to Claim 18, wherein a diazotised
amino compound of the formula (2), a coupling component of the
formula (3) and an aminobenzene of the formula (5), in which
A is an ortho-hydroxy-mono- or -di-sulphobenzene radical,
m = 1, n = 1, p = 0 and X is methyl, methoxy, carboxyl or
chlorine, and in addition an agent which donates copper are
used as the starting materials.
28. Process according to Claim 18, wherein a diazotised
amino compound of the formula (2), a coupling component of the
formula (3) and an aminobenzene of the formula (5), in which
A is an ortho-hydroxy-disulphobenzene radical, m = 1, n = 0 and
X is methyl, methoxy, carboxyl or chlorine, and in addition an
agent which donates copper are used as the starting materials.
32

29. Process according to Claim 18, wherein a diazotised
amino compound of the formula (2), a coupling component of the
formula (3) and an aminobenzene of the formula (5), in which A
is an ortho-hydroxy-disulphophenylazobenzene radical, m = 1,
n = 0 and X is methyl, methoxy, carboxyl or chlorine, and in
addition an agent which donates copper are used as the
starting materials.
30. Process according to Claim 18, wherein a diazotised
amino compound of the formula (2), a coupling component of the
formula (3) and an aminobenzene of the formula (5), in which A
is an ortho-hydroxy-disulphonaphthalene radical, m = 2, n = 0
and X is methyl, methoxy, carboxyl or chlorine, and in addition
an agent which donates copper are used as the starting materials.
31. Process according to Claim 18, wherein a diazotised
amino compound of the formula (2), a coupling component of the
formula (3) and an aminobenzene of the formula (5), in which A
is sulphophenyl, m = 2, n = 1, p = 1 and X is methyl, methoxy,
carboxyl or chlorine, are used as the starting materials.
32. Process according to Claim 18, wherein a diazotised
amino compound of the formula (2), a coupling component of the
formula (3) and an aminobenzene of the formu1a (5), in which A
is di- or tri-sulphonaphthyl-2, m = 1, n = 0 and X is methyl,
methoxy, carboxyl or chlorine, are used as the starting materials.
33. Process according to Claim 18, wherein a diazotised
amino compound of the formula (2), a coupling component of the
formula (3) and an aminobenzene of the formula (5), in which A
33

is disulphonaphthyl-2, m = 2, n = 1, p = 1 and X is methyl,
methoxy, carboxyl or chlorine,are used as the starting materials.
34. Process according to Claim 18, wherein a diazotised amino
compound of the formula (2), a coupling component of the for-
mula (3) and an aminobenzene of the formula (5), in which A is
ortho-hydroxy-disulphonaphthyl-2, m = 2, n = 0 and X is methyl,
methoxy, carboxyl or chlorine, and in addition an agent which
donates copper are used as the starting materials.
35. Process according to Claim 32, wherein diazotised 2-amino-
naphthalene-1,5-disulphonic acid is coupled with 2-acetylamino-
5-hydroxynaphthalene-7-sulphonic acid and the acetyl group is
split off by saponification, the resulting azo compound is
subjected to a condensation reaction with 2,4,6-trifluoro-1,3,5-
triazine and the resulting primary condensation product is
subjected to a condensation reaction with 1-amino-2-methyl-
benzene to give the fibre-reactive azo dyestuff of the formula
<IMG> .
36. Process according to Claim 33, wherein diazotised 2-
aminonaphthalene-1,5-disulphonic acid is coupled with 1-(4'-
nitrobenzoylamino)-8-hydroxynaphthalene-3,6-disulphonic acid
and the nitro group is reduced to the amino group, the result-
int azo compound is subjected to a condensation reaction with
2,4,6-trifluoro-1,3,5-triazine and the resulting primary con-
34

densation product is subjected to a condensation reaction with 1-amino-2-
methylbenzene to give the fibre-reactive azo dyestuff of the formula
<IMG>
37. Process according to claim 34, wherein diazotised 2-amino-1-
hydroxynaphthalene-4,8-disulphonic acid is coupled with 1-amino-8-hydroxy-
naphthalene-3,6-disulphonic acid and the resulting azo compound is treated
with an agent which donates copper, the resulting copper complex is sub-
jected to a condensation reaction with 2,4,6-trifluoro-1,3,5-triazine and
the resulting primary condensation product is subjected to a condensation
reaction with 1-amino-2-methyl-benzene to give the copper complex compound
of the fibre-reactive azo dyestuff of the formula
<IMG>
38. Process for dyeing and printing using a fibre-reactive azo dye-
stuff according to claim 1.
39. Process according to claim 38, for dyeing cellulose fibres.

40. Dyeing and printing formulations which contain fibre-reactive
azo dyestuffs according to claim 1, 2 or 3.
41. The dyed or printed textile material obtained according to claims
38 and 39.
42. Dyeing and printing formulations which contain fibre-reactive
azo dyestuffs according to claim 4, 5 or 6.
43. Dyeing and printing formulations which contain fibre-reactive
azo dyestuffs according to claim 7, 8 or 9.
44. Dyeing and printing formulations which contain fibre-reactive
azo dyestuffs according to claim 10, 11 or 12.
45. Dyeing and printing formulations which contain fibre-reactive
azo dyestuffs according to claim 13, 14 or 15.
46. Dyeing and printing formulations which contain fibre-reactive
azo dyestuffs according to claim 16 or 17.
36

Description

~7~2~
The present invention relates to a fibre-reactive azo dyestuff of
the formula
HO
A-N=N ~ ~ `f ~ (S3H)m F (1)
N N
~ C~ _ ~ NH ~ C~ N ~C ~
in which A is a benzene or naphthalene radical, X is alkyl or alkoxy with 1
to 4 carbon atoms, carboxyl or halogen, m is 1 or 2, n is O or 1 and p is O
or 1, it being possible for A and the benzene radical B to contain as further
substituents sulfo, alkyl groups with 1 to 4 carbon atoms, alkoxy groups with
1 to 4 carbon atoms, acylamino groups with 1 to 6 carbon atoms~ amino groups,
ureido, nitro, methysulfonyl, hydroxy, carboxy and halogen, and A is also
sulfophenylazo; and the metal complexes of the fibre-reactive azo dyestuffs
of the formula ~1).
For X, possible alkyl groups with 1 to 4 carbon atoms are: methyl,
ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl and tert.-butyl,
possible alkoxy groups with 1 to 4 carbon atoms are: methoxy, ethoxy,
propoxy, isopropoxy, butoxy, isobutoxy, sec.-butoxy and tert.-butoxy, and
possible halogen atoms are: fluorine, chlorine and bromine.
. .
- 2 -
.

3 ~7~Z~L
n~ ~rv~
Fibre-reactive azo dyestuffs of the formula (1) i-n
which A, B,m, n and p have the meanings indicated and X i.s
me-thyl, me-thoxy, carboxyl or chlorine are preferred.
Importa.n-t sub-groups o:E the fibre-reac-tive azo dye-
s-tu~fs o.~ the formula (1) are charac-terised as follows:
a) A is a mono- or di-sulphobenzene radical, m is 1 or 2 and
n - O,
b) A is a mono- or di-sulphobenzene radical or a carboxybenz-
ene radical, m = 2, n = 1 and p = 1,
c) A is a di- or -tri-sulphonaphthalene radical, m = 1 and n =
O,
d) A is a di- or trisulphonaphthalene radical, m = 2, n = 1
and p = 1,
e) copper complex compounds, A is an ortho-hydroxy-mono- or
-di-sulphobenzene radical, m = 1, n = 1 and p = O,
f) copper complex compounds, A is an or-tho-hydroxy-disulpho-
benzene radical, m = 1 and n = O,
g) copper complex compounds, A is an ortho-hydroxy-disulpho-
phenylazobenzene radical, m = 1 and n = O,
h) copper complex compounds, A is an ortho-hydroxy-disulpho-
naphthalene radical~ m = 2 and n = O,
i) A is sulphophenyl, m = 2, n = 1 and p = 1 9
j) A is di- or tri-sulphonaphthyl-2, m = 1 and n = O,
k) A is disulphonaphthyl-2, m = 2, n = 1 and p = 1 and
1) A is ortho-hydroxy-disulphonaphthyl-2, m = 2 and n = 3,
X being methyl, me-thoxy, carboxyl or chlorine in all the cases
-- 3 --
.. .. . . . . .. . .. .. . .. . .
~' ' -' .

7~ii2~
a) to 1) mentioned
Valuable flbre-reactive azo dyestuffs of the formula
(1) are, for example, the fibre-reactive azo dyestuff of the
formula
S05H H0
~ H0 S ~ ~ ~ V
Csub-group c)~ and the fibre-reactive azo dyes-tuff of the
forrnula
S03H H0 N~I-C ~ ~H-C~`e-~E
I~=N ~ N~,N CH
H03S ~ S03X
. S03H
[sub-group k)].
The dyestuffs of -the formula (1) are fibre-reactive
since they contaln, in the s-triazine radical, a fluorine atom
which can be split off.
Fibre-reactive compounds are to be understood as -those
:. which are capable of reacting with the hydroxyl groups of
- cellulose or with the amino groups of natural or syn-thetic
polyamides, with the formation of covalent chemical bonds.
: The fibre-reac-tive azo dyestuffs of the :Eormula (1) are
~ rnanufactured by a process wherein a diazotised amino compound of
'~
_ 4 ~
.
, . -`, ``` . .. , ~, . . . . .
.
, . ' `
,

the formula
A-NH2 (2)
a coupling componen-t of -the formula
HO
S03H)m . (3)
H {-~C~ ~ ~--NH-~-n-H
2,4,6-tri.fluoro-1,3,5-triazine of -the formula
. ~
N~'C`N (4)
11
~--C~,C--F
and an aminobenzene of the formula
2 ~ (5)
X
are reacted, by coupling:and condensa-tion, in any desired
sequence to give a fibre-reactive azo dyestuff of the formula
(1), -
An aminobenzene of the formula (5~ in which X is methyl,
methoxy, carboxyl or chlorine is preferably used as the s-tar-t-
.,
: ing material.
In preferred embodiments of the process described above,
diazo components of -the formula (2) and coupling components of
the formula (3) in which A, m, n and p have the same meanings
- 5 -
., ~ , , - .

~7~
as in the sub-groups a) to 1), listed above, a~d in all cases,
aminobenzenes of the formu].a (5) in ~Jhich X is methyl, metho~.y,
carboxyl or chlorine are used as the starting materials.
Since -the .individual process steps indicated above can
be carried out in various sequences, optionally also si.mul-
taneously in some cases, dif:Eerent process varlants are possible.
The s-tarting materials to be used for each part reac-tion are
given by formula (l). In general, -the reaction is carried
out stepwise successively, it being possible -to choose freely
the sequence of the simplé reactions between the individual
reactants of the formulae (2) 7 ~3), (4) and (5).
- ~ -Impor-tant process varian-ts are those wherein
l) a diazotised amino compound of the formula (2~ is coupled
wi-th a coupling componen-t of -the formula (3) -to give an azo
compound of the formula
~
A-N=N ~ 3 )m (6)
~- r(C ~ } -A~-~n-Tri
this is subjected to a condensation reaction wlth 2,4~6-tri-
fluoro-1,3,5-triazine of the formula (4) and the primary
condensation product obtained is subjected to a condensation
reaction wi-th an aminobenzene of the formula (5) to give a
fibre-reactive azo dyestuff of the formula (l);
2) ~ coupling component ~ -the formula (3) is subjected to a
condensation reaction wi-th 2,4,6-trifluoro-1,3,5-triazine of
. .
-- 6 --
.
:,
" : :.

2~a
the ~ormula (4), ~he resulting primary condensation product is
subjected -to a condensa-tion reaction with an aminobenzene o~
the :Eormula (5) and the secondary condensation produc-t formed
is coupled with a diazotised amino compound o~ the formula (2)
-to give a ~ibre-reac-tive azo dyestu:E:~ o~ the ~ormula (l); and
3) a coupling componen-t o~ the ~ormula (3) is subjected to a
condensa-tion reac-tion with 2,4,6-tri~luoro-1,3,5--triazine of
-the formula (4), a diazotised amino compound o:E the formula (2)
is coupled to the resul-ting primary condensation product and the
resulting azo compound is subjected to a condensa-tion reaction
wlth an aminobenzene of the formula (5) to give a fibre-reactive
azo dyestu~ of -the ~ormula (1).
S-tar-ting ma-terials which may be mentioned which can be
used for the manufacture of the fibre-reac-tive azo dyes-tuffs
o~ -the formula (1) are:
~ c7-~-o~
l~aminobenzene-2-, -3- and -4~sulphonic acid, l-amino-
benzene-2,4- and -2,5-disulphonic acid, 1-amino-4-me-thylbenz-
ene-2-sulphonic acid, 1-amino~3-methyl~enzene-6-sulphonic acid,
l-amino-6-me-thylbenzene-3- or -4-sulphonic acid, 1-amin~-2,4-
dime~hylbenzene-6-sulphonic acid, 1-amino-2-carboxybenzene-4-
sulphonic acid, l-amino-4-carboxybenzene-2-sulphonic acid,
l-amino-4- or -5-chlorobenzene--2 sulphonic acid, 1-amino-6-
chlorobenzeDe-3- or -4-sulphonic acid, 1-amino-3,4-dichloro-
benzene-6-sulphonic acid, 1-amino-2,5-dichlorobenzene-4-sulph-
onic acid, l-amino-4-me-thyl-5-chlorobenzene-2-sulphonic acid,
l-amino-5-methyl-4-chlorobenzene-2 sulphonic acid, 1 amino-4
- 7 -

~3ca7~
or -5-me-thoY~ybenzene-2-sulphonic acid, 1-arnino-5-Methoxyben~ene-
3- or -4-sulphonic acid, 1-amino-6-ethoxybenzene-3- or 4-
sulphonic acid, l-amino-2,LI--dimethoxybenzene-6-sulphonic acid,
l-amino-2,5-dirne-thoxy~enzene-~-sulphonic acid, 1-amino-3-
ace-tylaminoben7.ene-6-sulphonic acid, l-amino-~-acetylamino-
benzene-2-sulphonic acid, 1-amino-3-acetylamino-~-methylbenzene-
6-sulphonic acld, 1-aminonaph-thalene-2-, -~-, -5-, -6-, -7-
or -8-sulphonlc acid, 2--aminonaphthalene-1-, -5- or -6-sulph-
onic acid, l-aminonaph-thalene-~,6- or -5,7-disulphonic acid,
2-aminonaphthalene-1,5-, -1,7-, -3,6-, -5,7-, -4,8- or -6,8-
disulphonic acid, l-aminonaph-thalene-2,5,7-trisulphonic acid,
2-aminonaphthalene-1,5,7-~ -~,6,8- or -L~,6,8-trisulphonic acid,
l-hydroxy-2-aminobenzene-L~-sulphoni.c acid, l-hydroxy-2-amino-
~enzene-5-sulphoni.c acid, 1-hydroxy-2-aminobenzene-4,6-di-
sulphonic acid, l-hydroxy-2-amino-4-acetylaminobenzene-6-
sulphonic acid, ].-hydroxy-2-amino-6-acetylaminobenzene-4-sulph-
onic acid, l-hydroxy-2-amino-4-chlorobenzene-5-sulphonic acid,
l-hydroxy-2-amino-4-me-thylsulphonyl-benzene, 1-amino-2-hydroxy-
6-nitronaphthalene-4-sulphonic acid a-nd 2-amino-1-hydroxy-
naphthalene-~,8-di.sulphonic acid.
- 2-arnino-5-hydroxynaph-thalene-7-sulphonic acid, 2-methyl-
or -ethyl-amino-5-hydroxynaphthalene-7-sulphonic acid, 2-(N-
acetyl-N-rnethylamino)-5-hydroxynaphthalene-7-sulphonic acid,
2-acetylamino-5-hydroxynaphtha].ene-7-sulphonic acid, 2-amino-5-
hydroxynaphthalene-1,7-disulphonic acid, 2-amino-8-hydroxy-
naphthalene-6-sulphonic acid, 2-methyl- or ethyl-amino-8-
-- 8 --
.
- .
. , ~ `
.
,' " ` ;' . `

~7~2~
hydro~ynaphthalene 6-su]phonic acid, 2-(N-acetyl-N--methy~ rlino)-
~~hydroxynaphthalene-6-sulphonic acid, 2-acetylamino-8-hydroxy-
naphthalene-6-sulphonic acid, 2-amino-~-hydroxynaphthalene-3,~-
disulphonic acid, 2-acetylamino-~-hydroxynaphthalene-3,6-
disulphonic acid, l--amino-5-hydroxynaph-thalene-7-sulphonic acid,
l-amino-~-hydroxynaphthalene-3,6- or -~,6-di.sulphonic acid, l-
acetylamino-8-hydroxynaph-tha].ene-3,6- or -~,6-disulphonic acid,
l-(4~-aminobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-
disulphonic acid, 1-(4'-nitrobenzoylamino)-8-hydroxynaphthalene-
3,6- or -4,6-disulphonic acid, 1-(3'-aminobenzoylamino)-8-
hydroxynaphthalene-3,6- or -4,6-disulphonic acid, l-(3'-
ni-trobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-disulphonic
acid and 2-(4'-amino-3'-sulphophenylamino)-5-hydroxynaph-thalene-
7-sulphonic acid.
2 4 6-Trifluoro-l 3 5-triazine (cyan r.~ 'I.or'~ r _
formula ~)
l-amino-2-methyl-, -e-thyl- or -propyl-benzene, l-amino-
2-methoxy- or -ethoxy-benzene, l-amino-2-carboxybenzene, l-
amino-2-chlorobenzene, l-amino-2-bromobenzene and l~amino-2-
fluorobenzene.
As a rule, the diazo-tisati.on of the amino compounds of
the formula-(2) is carried out by the action of nitrous acid
in an aqueous-mineral acid solution at a low temperature and
the coupling to the coupling cornponen-ts ofthe ~ormula (~) is
carried out at weakly acid, neutral -to weakly alkaline pH
values.
- _ g .

The condensa-tion reac-tio-ns of 2,4,6--trlfluoro-1,3,5-
triazine wi-th the coupling components of the forrnula (3) or
wi-th -the a~o compounds of the formula (6) and the aminobenzenes
of the formula (5) are preferably carried ou-t in an aqueous
solution or suspen.s:ion, at a ]ow -temperature and at a weakly
acid, neutral -to weakly alkaline p~I value. The hydrogen
fluoride liberated during the condensation reac-tion is advan-
tageously continuously neutralised by adding aqueous alkali
me-tal hydroxides, carbonates or bicarbonates.
If the benzene or naphthalene radical A in the ortho-
posi-tion to the azo group con-tains a complex-forming group, for
example a hydroxyl or carboxyl group, metal complexes o~ -the
fibre-reactive azo dyestuffs of -the formula (1) can also be
manufactured. Copper complexes are of particular interes-t;
they are manufac-tured by treating azo compounds of -the formula
(6) in which ~ is a benzene or naphthalene radical which con-
tains a complex-forming group in the ortho-position -to the azo
group, before or optionally also after the acylation with
2,4,6-trifluoro-1,3,5-triazine of the formula (4)l with agents
which dona-te copper.
. A method which can be used for coppering is not only
the-me-thod descrlbed above, in:which a o,o'-dihydroxyazo com-
pound is used as the starting material for the complex form-
ationJ but also oxidati~e coppering, in which the hydroxyl
group required for complex formation is introduced in-to the
naph-thalene nucleus only during -the coppering action, by the
simultaneous action of an oxidising agent. Instead of a
-- 10 --
.

7~
l-hydroxy 2-arnino-naphthalene-4,8-disulphonic acid, for e~ample,
the correspondi.ng 2-amino-naph-tha.Lene-4,8-disulphonic aci~ is
-then used as the dla~o component.
However, diazo componen-ts which contain, instead of a
hydroxyl group, in the l-position of a naphthalene nucleus, an
alkoxy group, in par-ticular the methoxy group, which can be
conver-ted into -the hydroxyl group by spli-t-ting off the alkyl
raaical, under suitable reaction conditions, during the copper-
ing reaction, c~n also be used for the manufac-ture of the com-
pounds of the formula (1).
~ gents which can be used which dona-te copper are, for
example, salts which contain copper as a cation, such as, for
example, copper sulphate and copper ace-ta-te. In some
cases it is advan-tageous -to use complex copper compounds, for
example in -the form of cuprammine complexes, such as -tetrammine~
-copper sulphates ~rom copper sulphate and ammonia, pyridine or
monoethanolamine, or in -the form of compounds which contain cop-
per bo~ded in a complex 9 ~or example complex copper compounds
of the alkali me-tal salts of alipha-tic aminocarboxylic acids
or hydroxycarboxylic acids, such as o~ glycine, of lace-tic acid
and, above all, of tartaric acid, such as sodium copper tartrate.
The treatment with the agent ~hich dona-tes copper can
be carried out by methods which are in themselves known, for
example at room temperature if starting compounds which can be
easily metallised are present or, if dealkylation must take
place simultaneously with the metallisa-tion, by warming -to
temperatures between 50 and 12~C in an open vessel, for example

~ 7~
wi-th reflux cooling, or optionally in a closed vessel under
pressure, the pH conditions being given by the nat~re o~ -the
me-tallising process chosen; for example an acid coppering ~i-th
copper sulpha~te and all alkaline coppering wi-th -tetrammine-
copper sulphate If desired, solven-ts, such as, for
example, alcohol, dime~thy:lformamide and -the like, can also be
added during -the metal:lisa-tion. In the case of oxida-tive
coppering, an oxidising agen-t, in particular hydrogen peroxide,
is also added to the reac-tion mix-ture and in other respects
-the reaction is carried out in the manner described
The fibre-reacti~e azo dyestu~fs of the formula (I) are
distinguished by a high reactivi-ty and a high degree of fixing.
They are suitable for dyeing and prin-ting -the most
diverse ma-terials, such as silk, lea-ther, wool, high molecular
weigh-t polyamide fibres and high molecular weigh-t polyurethanes,
bu-t in particular cellulose--containing ma-terials having a
fibrous structure, such as linen, cellulose, regenera-ted
cellulose and, above all, cot-ton. They are suitable both
for the exhaustion process and for dyeing by -the pad-dyeing
process, by whi.ch the goods are impregnated with aqueous dye-
stuff solutions, which optionally also contain salts, and the
dyestuffs are fixed, after treatment with an alkali or in the
presence of alkali, if appropria-te with the ac-tion of heat.
They are also sui-table for printing, in particular on
cotton, but also are similarly suitable for printing ni-trogen-
con-taining ~ibres, for example wool, silk or mixed fabrics
containing wool.
- - 12 -
!
'

62~
.It i.s advisable to subject the clyeings and prin-ts to
a thorough rinsing wi-th cold and hot wa-ter, if appropriate
wi-th the addi~tion of an agen-t whlch has a dispersing action
and which ~)romo-tes dif~usiorl o~ -the non-fixed por-tions.
In the ~o:Llowing examples, par-ts deno-te par-ts by weight
and ~the -temperatures are given in degrees Cen-tigrade.
_a~
lL~ parts of 2,4,6--trifluoro-1,395-triazine are added
dropwise -to an aqueous solution con-taining 72.1 parts o~ ~the
dyestuff of the formula
3 HO
=N - ~ ~ Na~
~O~S ~0~ -03S/~V~ 2 l
at O to 5 in the course of 15 minutes, the pH value being kept
between 5 and 6 by sirnultaneously adding sodium hydroxide solu-
tion. After the condensation reaction has ended, 10.7 parts
o~ l-amino-2-me-thylbenzene are added, the mixture is allowed to
warm to roorn temperature and the pH value is kept at 6 to 7.
Sodium chloride is added to the red dyestuf'f solution and ~he
dyes-tuff o~ the formula
~1
-- ~03Na HO
~zo~s ~ ;~ N~----N~
. CH~
- 13 -

~3"7~
which has preci.pitated is fil-tered off and5 af-ter adding 2.5
parts of sodiu~n bicarbonate, dried. It dyes co-t~on, from an
aqueous ba-th, ln luminous scarlet shades of excellent fastness
-to we-t processing.
Ins-tead of sal-tlng ou-t, -the d.yestuff can also be
isola-ted. by evapora-ting the reac-tion mixture or by spray-
drying.
~ f an equivalent amount of l-amino-2-eth~lbenzene, 1-
amino-2-me-thoxybenzene5 1-amino-2-ethoxybenzene, 1-amino-2-
carboxybenzene, l-amino-2 chlorobenzene 5 1-ami.no-2-bromobenzene
or l-amino-2-fluorobenzene is used. instead of 1-amino-2-
me-thylbenzene, dyestuffs with similar coloristic properties
are obtained.
If -the aminoazo dyes-tuffs indicated in Table 1 which
follows are used instead of -the ami.noazo dyes-tuff given in the
example and l-amino-2-methylbenzene or an equivalent amount of
l-amino-2-e-thylbenzene 5 1-amino-2-methoxybenzene 5 1-amino-2-
: ethoxybenzene, l-amino-2-carboxybenzene 7 1-amino-2 chloro-
benzene, l-amino-2-bromobenzene or 1-amino-2-fluorobenzene is
used as the aminobenzene of the formula (5~ further valuable
dyestuffs which dye cellulose fibres in the shade indicated
are obtained.
. - 14 -
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~f~ 62~
Exarn~
13.5 par-ts of 2,~,6~trifluoro-153,5--triazine are added
dropwise -to an aqueous solu-t:ion of 48.2 par-ts of disodium 1-
(~'-aminobenzoylamino)-8-hydroxynaph-thalene-3,6-disulphonate
at 0 -to 5 and -the p~ va]ue :is kept between 5 and 6 by simul~
-taneously adding sodium hydroxide solution. In order to
dissolve the condensation produc-t, a diazo solution, prepared
~rom 25.3 parts of 1-aminobenzene-2~5-disulphonic acid in -the
cus-tomary manner, is now added and -the coupling reaction is
carried ou-t at a pH value of 7 to 7.5. After the coupling
reac-tion has ended, 10.7 parts of 1-amino-2-rnethylbenzene are
added, -the mix-ture is allowed to warm to room tempera-ture and
-the hydrogen fluoride llbera-ted during the condensation reaction
is continuously neu-tralised by adding dilute sodium hydroxide
solution. After the reaction has ended, the dyestuff is
precipi-tated by sprin~ling in sodium chloride, fll-tered off
and dried. It dyes fabrics of cellulose material in fast
brillian-t red shades.
If equivalent parts of -the coupling components listed
in the second column of Table 2 which follows are used instead
of 1-(3l-aminobenzoylamino)-8-hydroxynaphthalene~396-disulphonic
acid9 equivalent parts of -the diazo components given in the
third column are used instead of l-aminobenzene-2 9 5-disulphonic
acid and e~uivalen-t parts of ~the aminobenzenes given in the
fourth column are used instead o~ l~amino~2-me-thylbenzene, dye-
stuffs which dye cotton in -the shades given in the fif-th
colu~n are obtained.
-- 19 --
.
- ~

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~ 20 --
.

2~
Æxa~
-
l~.8 parts o~ disodium 1-(4'-aminobenzoylamino)-8-
hydroxynaph-thalene-4~6-disulphonate are dissolved in 700 parts
o~ wa-ter to give a neu-tral solu-tion. 13.5 par-ts of 2,4,6-
trifluoro--1,3,5---triazine are ad~ed dropwise to this solution
at O -to 5 and a-t a pH value o~ ~.5 -to 5 in the course of 15
minu-tes. The hydrogen fluoride libera-ted during the conden-
sa-t.ion reac-tion is continuously neutralised by adding ~ilute
sodium hydroxide solu-tion. Af-ter -the reac-tion has ended,
10.7 par-ts of 1-amino~2~methylbenzene are added and the pH
value is kep-t between 4.5 and 5.5, whils-t gradually warming the
mix-ture to room temperature. ~fter -the reac-tion has ended,
a suspension, adjus-ted to a pH value of 4 wi-th sodium carbonate,
of 30.3 par-ts of diazo-tised 2-aminonaph-thalene-1,5-disulphonic
acid is allowed to run in, whilst simul-taneously increasing the
pH value to ~. The dyes-tu:~f formed is precipi-ta-ted by
sprinkling in sodium chloride, filtered of~ and dried. I-t
is a dark red powder and dyes fabrics of cellulose ma-terial in
fast brillian-t red shades.
~ urther dyes-tuffs with similar properties are obtained
when equivalen-t parts o~ the coupling components, which can be
acylated, listed in the second column in Table 3 which follows
are subjec-ted to a condensation reaction with 2,4,6--trifluoro-
1,3y5--triazine according to the .instructions in the p~eceding
example, the condensation produc-t is then reacted with equiva-
lent par-ts of -the aminobenzenes listed in the third column and
the reaction produc-ts are -then combined with the diazo com-
~ 21 --
" '~ . '' ~ ~ ' ' .

~7~i2~L
ponen-ts given in -the fourth col~unn.
22
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2 parts of -the dyes-tuff obtained according -to E~ample
1 are dissolved ln 100 parts of water, wi-th the addition of
0~5 par-t of sodium m~nitrobenzene~ulphonate. A cotton
fabric is impregna-tecl wi-th the resulting solution, so -that i-ts
weight increases by 75~, and then dried.
Thereaf~ter, -the fabrlc is impregnated with a solu-tion,
warmed to 20, containing 5 grams of sodium hydroYide and
300 grams of sodium chlor~de per li-tre and squeezed out to a
weight increase of 75%, -the dyeing is s-teamed for 30 seconds
at 100 to 101, rinsed, soaped for quar-ter of an hour in a
0.3% streng-th boiling solution o~ a non-ionic washing agen-t,
rinsed and dried.
Dyeing Instructions~
2 parts of the dyes-tuff obtainable according to Example
1 are dissolved in 100 parts of water.
The solu-tion is added to 1,900 parts of cold wa-ter,
60 parts of sodium chloride are added and 100 parts of a cotton
fabric are pu-t into this dye bath.
The temperature is increased -to 40, 40 par-ts of
calcined sodium carbonate and a further 60 par-ts of sodium
chloride being added after 30 minutes. I'he -temperature is
kept at 40o for 30 minutes and the dyeing is rinsed and -then
soaped for 15 minutes in a 0.3% streng-th boiling solution of a
non-ionic washing agent, rinsed and dried.
- 24 -