DYESTUFFS, THEIR PREPARATION AND USE

MODES DE PREPARATION ET D'EMPLOI DE MATIERES COLORANTES

English Abstract

Abstract of the Disclosure

New reactive dyestuffs having the formula I

Image

wherein F denotes the radical of a dyestuff, X denotes a
substituent which can be split off as an anion, Z is a
.beta.-halogenoethyl radical or vinyl radical, R and Vn denote
each hydrogen and/or the radical of a hydrocarbon and p
and m are each 1 and/or 2 and n is 2 minus m, their prepa-
ration and use for the dyeing of cellulose or polyamide
containing textile material in shades of outstanding
fastness properties.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A reactive dyestuff of the formula I

Image I

wherein F denotes the radical of a dyestuff which contains at least one
-SO3H group, R denotes hydrogen or lower alkyl, X denotes a substituent
which can be split off as an anion, p denotes 1 or 2 and A denotes a
radical of the formula II

Image II

in which alk is a lower alkylene radical having 2 - 6 C atoms and V is
hydrogen or a methyl group optionally substituted by a carboxylic or sul-
phonic acid group or derivative thereof, or is an alkyl radical which
has 2 - 6 C atoms and is optionally substituted by at least one alkoxy
group having 1 or 2 C atoms, a carboxylic or sulphonic acid group, halogen
atom or hydroxyl group, or is an unsubstituted alkyl radical having 7 -
20 C atoms, a cyclohexyl radical or a phenyl radical optionally substituted
by at least one methyl, ethyl, methoxy, ethoxy, carboxylic acid or sul-
phonic acid group or halogen atom, Z is a .beta.-halogenoethyl radical or a
vinyl radical, m is 1 or 2 and n is 2 minus m.

2. A reactive dyestuff as claimed in claim 1 wherein F is a
radical of a metal-free or metal containing monoazo or disazo dyestuff
which contains at least one -SO3H group; a radical of a derivative of 1-
amino-anthraquinone or 1-anilino-anthraquinone; a radical of a sulpho-
phthalocyanine dyestuff; or a radical of a formazan or nitroaryl dye-
stuff.

78


3. A reactive dyestuff as claimed in claim 2 wherein F is a
radical of a metal-free or metal containing monoazo or disazo dyestuff
which contains at least one -SO3H group.

4. A reactive dyestuff as claimed in claim 3 wherein F is a radical
of a monoazo or disazo dyestuff of the formula VIa, VIb or VIc.

D-N=N-(M-N=N-)n K- (VIa)
-D-N=N-(M-N=N-)n K
-D-N=N-(M-N=N-)n K- (VIc)

or of a metal complex derived therefrom, in which formulae VIa, VIb and
VIc, D represents the radical of a diazo component of the benzene or
naphthalene series, K represents the radical of a coupling component of
the benzene, naphthalene or ketomethylene series, M represents the radical
of a middle component of the benzene or naphthalene series, n represents
the number 0 or 1 and D, M and K together contain at least two sulphonic
acid groups.

5. A reactive dyestuff as claimed in claim 4 wherein each of D,
K and M is substituted by at least one substituent selected from hydroxyl,
methyl, ethyl, methoxy or ethoxy, alkanoylamino having 2 - 4 C atoms, ben-
zoylamino or halogen.

6. A reactive dyestuff as claimed in claim 4 wherein D, M and K
together contain three or four sulphonic acid groups.

7. A reactive dyestuff as claimed in any of claims 4 to 6

79


wherein K represents the radical of a coupling component of the benzene,
naphthalene, pyrazolone, 6-hydroxypyrid-2-one or acetoacetic acid arylamide
series.

8. A reactive dyestuff as claimed in claim 2, characterised in that F
is a radical of a derivative of 1-amino-anthraquinone or 1-anilino-anthra-
quinone.

9. A reactive dyestuff as claimed in claim 8 wherein F is a radical of
an anthraquinone dyestuff of the general formula VII

Image (VII)

wherein Z represents a phenylene radical, at least one of the anthraquinone
nucleus and the phenylene radical being optionally substituted by a further
- SO3H group, and the phenylene radical being optionally substituted by a
carboxyl group, an alkoxy group having 1-3 C atoms, a halogen atom or by 1-3
alkyl groups each having 1-3 C atoms.

10. A reactive dyestuff as claimed in claim 2, wherein F is a radical
of a sulphophthalocyanine dyestuff.

11. A reactive dyestuff as claimed in claim 10 wherein F is a radical of
a phthalocyanine dyestuff of the general formula VIII

Image VIII

wherein Pc represents the radical of a metal-containing or metal-free phthalo-
cyanine, each W represents hydroxyl or NR'R", and each of R', R" and R"'
which may be the same or different, is hydrogen or alkyl having 1-4 C atoms,




B denotes a phenyl radical optionally substituted by halogen, by 1-3 alyyl
groups each having 1-2 C atoms, or by one or two sulphonic acid groups or
carboxylic acid groups, or denotes an alkyl radical having 2-6 C atoms or the
ethylene radical, k denotes 2 or 3 and p denotes 1 or 2.

12. A reactive dyestuff as claimed in claim 11 wherein the metal-con-
taining phthalocyanine is copper or nickel phthalocyanine.

13. A reactive dyestuff as claimed in claim 11 or claim 12 wherein B is
phenyl substituted by a sulphonic acid group.

14. A reactive dyestuff as claimed in claim 11 wherein F is a derivative
of a phthalocyaninesulphanilide or phthalocyaninesulphalkylamide which has
2-6 C atoms in the alkyl chain and carries at least two sulphonic acid groups
in the phthalocyanine nucleus.

15. A reactive dyestuff as claimed in claim 1, 9 or 11 wherein R denotes
hydrogen or alkyl which has 1 to 4 C atoms and is optionally substituted by
-COOH or -SO3H, or denotes cyanoethyl or hydroxyethyl.

16. A reactive dyestuff as claimed in claim 1, 9 or 11 wherein R is
hydrogen or methyl.

17. A reactive dyestuff as claimed in claim 1, 9 or 11 wherein X re-
presents fluorine, chlorine, bromine, alkylsulphonyl having 1 to 4 C atoms,
phenylsulphonyl or the -SO3H radical.

18. A reactive dyestuff as claimed in claim 1, 9 or 11 wherein X re-
presents chlorine.

19. A reactive dyestuff as claimed in claim 1 wherein in general formula
II alk denotes a methylene, ethylene, or a straight or branched chain isomer
of a polymethylene radical having 3 to 6 C atoms.

20. A reactive dyestuff as claimed in claim 19, wherein alk denotes an
ethylene radical.

81


21. A reactive dyestuff as claimed in claim 1 wherein V denotes
hydrogen or an alkyl radical having 1 to 4 C atoms optionally substituted
as defined in claim 1.

22. A reactive dyestuff as claimed in claim 21 wherein V denotes
hydrogen or methyl.

23. A reactive dyestuff as claimed in claim 1 or 9 wherein Z is .beta.-
chloroethyl or vinyl and X represents chlorine or bromine.

24. A reactive dyestuff as claimed in claim 1 or 9 wherein X is
chlorine, alk is ethylene, Z is .beta.-chloroethyl or vinyl and m represents the
number 2.

25. A process for the preparation of a reactive dyestuff of the
formula I as defined in claim 1 wherein a dyestuff of the formula V


Image V


wherein F, R and p each have the same meaning as defined above in formula I
and X and X', which are the same or different, each have the meaning as
defined above for X in formula I, is reacted with an amine of the formula
IIa

Image IIa

wherein alk, Z, V, n and m have the same meaning as defined above in formula
I.

26. A process as claimed in claim 25 wherein the reaction is carried
out at a temperature in the range from 25 to 70°C, and in an aqueous medium
at a pH value in the range from 2 to 6.5.

82


27. A process as claimed in claim 26 wherein the reaction is carried
out at a temperature of from 35 to 55°C and at a pH value of from 3.5 to
4.5

28. A process as claimed in any of claims 25 to 27 which includes
the preliminary step of reacting a dyestuff of the formula III

Image III

in which F, R and P have the same meaning as defined above in formulae V,
with a reactive derivative of 1,3,5-triazine of the formula IV

Image IV

in which X and X' have the same meaning as defined above in formula V, so
as to produce a dyestuff of the general formula V.

29. A process as claimed in any of claims 25 to 27 which includes
the preliminary step of reacting a first dyestuff component which contains
a radical of the formula Va

Image Va

in which R, X and X' have the same meaning as defined above in formula V,
with a second dyestuff component which optionally contains a radical of the
formula Va as defined above, so as to produce a dyestuff of the formula V
as defined above.

30. A process as claimed in any of claims 25 to 27 wherein in formula
V, F is a radical of a metal-free or metal-containing monoazo or disazo dye-
stuff, which process includes the preliminary step of reacting a diazo
component and a coupling component, at least one of which contains a group

83


of the formula Va, so as to produce said compound of formula V.

31. A method of dyeing or printing a cellulose, natural or synthetic
polyamide substrate or a material containing a said substrate, which com-
prises applying to said substrate or material a reactive dyestuff as claimed
in claim 1 or 9.

84

Description

1~7~72

The invention relates to new, valuable reactive dyestuffs
of the formula I



F
~ P
_ X
; wherein F denotes the radical of a dyestuff which contains at least one
-S03H group, R denotes hydrogen or lower alkyl, X denotes a substituent
which can be split off as an anion, p. denotes 1 or 2 and A denotes a
radical of the formula II

/ (alk - S02 - Z)
N II
\Vn
in which alk is a lower alkylene radical having 2 - 6 C atoms and V
is hydrogen or a methyl group optionally substituted by a carboxylic
or sulphonic acid group or derivative thereof, or is an alkyl radical
which has 2 - 6 C atoms and is optionally substituted by at least one
alkoxy group having 1 or 2 C atoms, a carboxylic or sulphonic acid
group, halogen atom or hydroxyl group, or is an unsubstituted alkyl
radical having 7 - 20 C atoms, a cyclohexyl radical or a phenyl radical
optionally substituted by at least one methyl, ethyl,methoxy, ethoxy,
carboxylic acid or sulphonic acid group or halogen atom, Z is a ~-halo-
genoethyl radical or a vinyl radical, m is 1 or 2 and n is 2 minus m.
Fibre-reactive dyestuffs are to be understood as dyestuffs
which are capable of reacting with the hydroxyl groups of cellulose
or with the reactive centres of natural or




B
~ . ................... . ~ .. . . .
. .. .. . .
.. . . . .

~ Ref, 3062
~; 10~7172 `

.
synthetic polyamides with the formation of covalent chemical
bonds. The radical F in formula I can be derived from any
known class of dyestuffs, it preferably belongs to the anthra-
quinone series, the metal-free or metal-containing monoazo
or disazo series, the phthalocyanine series, the formazan
series or the nitroaryl series. ~yestuffs, according to
the invention, in which F is a dyestuff radical of the anthra-
quinone series, the metal-free or metal-containing monoazo or
disazo series or the phthalocyanine series are preferred.
F preferably contains two to four sulphonic acid groups.
The substituent R is hydrogen or a straight-chain or
branched low-molecular alkyl group having 1 to 4 C atoms, such
as methyl, ethyl, propyl, isopropyl or n-butyl, 2-methyl-
propyl, sec.-butyl or tert.-butyl and also a substituted alkyl
radical, such as carboxymethyl, sulphomethyl, sulphoethyl,
cyanoethyl, ~-chloropropyl or ~-hydroxyethyl. The methyl
radiçal is preferred. Hydrogen is particularly preferred as
R.
Substituents which can be split off as an anion are
especially chlorine, bromine, fluorine, alkylsulphonyl, such
as methylsulphonyl or ethylsulphonyl, phenylsulphonyl or the
-S03H radical
X is preferably a chlorine atom.
The radical of the optionally substituted hydrocarbon -
V is especially a methyl group which is optionally substi-
tuted by the carboxyl group or the sulphonic acid group or
derivatives thereof, or an alkyl radical which has 2-6 C
atoms and is optionally substituted by alkoxy groups having 1




.

~~ Ref. 3062

l~B7~72

or 2 C atoms, by carboxyl or sulphonic acid groups or by halo-
gen atoms or hydroxyl groups, or an unsubstituted alkyl
radical having 7-20 C atoms, a cyclohexyl radical or a phenyl
radical which is optionally substituted by methyl, ethyl, meth-
oxy, ethoxy, carboxylic acid or sulphonic acid groups or by
halogen atoms.
The invention relates especially to dyestuffs accor-
ding to the formulae I and II in which Z represents the ~-
chloroethyl radical and X represents a halogen atom.
Those dyestuffs in which X represents a chlorine atom,
alk represents the ethyl radical, Z represents the ~-chloro-
ethyl radical and m represents 2 are a particularly preferred
group of dyestuffs according to the general formulae I and II.
In the case where m is equal to 2, the two radicals
-alk-S02-Z can be identical or, within the scope of the defi-
nitions of alk and Z, can be different. ~yestuffs in which
both radicals -alk-S02-Z are identical are preferred.
Lower alkylene radicals which can represent alk in A
are the ethylene radical, the trimethylene radical, the tetra-
methylene radical, the pentamethylene radical or the hexamethy-
lene radical as well as their branched isomers. The
ethylene radical is preferred.
The following radicals may be mentioned as examples
of V: hydrogen, methyl, carboxymethyl, carbomethoxymethyl,
carboethoxymethyl, sulphomethyl, sulphamidomethyl, ethyl,
carboxyethyl, sulphoethyl, propyl, ~-carboxypropyl, ~-
sulphatoethyl, ~-ethoxyethyl, ~-methoxypropyl, Y-chloropropyl,
Y-bromopropyl, butyl, isobutyl, pentyl, hexyl, nonyl, dodecyl,

Ref. 3062
~3q~72


hexadecyl, pentadecyl, cyclohexyl, phenyl, o-, m- or p-
chlorophenyl, o-, m- or p-sulphophenyl, o-methylphenyl,
p-methoxyphenyl, m-methylphenyl or p-ethylphenyl. The
optionally substituted alkyl radicals which have 1-4 C atoms
are preferred, hydrogen and the methyl radical are particu-
larly preferred.
The reactive dyestuffs of the general formula I are
manufactured by reacting a dyestuff of the formula V

F ~ ~ ~ X'~ V

.' P . .

in which F, R and p have the meanings indicated above and X
and X' independently of one another have one of the meanings
mentioned above for X, with an amine of the formula IIa
'~:
~(al~-S02-Z)m IIa
~UI .

!~ n
,
, ~ ~
in which alk, Z, V, n and m have the meaning indicated above.
The dyestuffs of the general formula V are manufactured
` by reacting a dyestuff of the ~ormula III
r 1 III
,~ F - _ N - ~
_ R _ P

in which F, R and p have the meaning indicated above, with a
reactive derivative of the 1,3,5-triazine of the formula IV

-- 4 --

~ Ref. 3062
; 1~8717Z



X ~ ~ X' IV
~f .



in which X and X' independently of one another have one of the
meanings indicated above for X.
The manufacture of the dyestuffs V and of the reactive
dyestuffs I according to the invention can also be combined
advantageou~ly with one another 80 that a dye~tuff of the form-
ula III is first reacted with a reactive derivative of the 1,3,5-
triazine of the formula IV to give the dyestuff V and the
latter is then reacted, without isolating the dyestuff V, with
an amine of the formula IIa to give a reactive dyestuff I accor-
ding to the invention. The reaction of the dyestuffs of
the formula III with the triazine derivatives of the formula
IV is appropriately carried out at low temperatures, say between
-2 and +10, preferably between 0 and 5, with the addition of
acid-binding agents, such as sodium hydroxide solution, sodium
carbonate or sodium bicarbonate, within a pH range between 1.5
and 9, preferably between 4 and 6.
Water which contains a certain proportion of organic
solvents, such as, for example, acetone, is preferably used
as the solvent. The reaction can, however, also be carried
out in pure water.
For the further reaction, with the amines of the form-
ula IIa, of the dyestuffs of the formula V which have been
obtained in this way, the amines are appropriately employed
in the form of a salt, preferably in the form of the

Ref. 3062
~37~7z

.
hydrochloride, The reaction is carried out at elevated
temperature, say between 25 and 70, preferably between 35
and 55, with the addition of acid-binding agents, preferably
sodium bicarbonate, within a pH range of 2-6.5, preferably
3.5 to 4.5.
If the dyestuff radical F is composed of several com-
ponents, such as is the case, for example, with azo dyestuffs
or formazan dyestuffs, the dyestuffs of the formula I accor-
ding to the invention can also be obtained by synthesising
them in a manner which is in itself known from components of
F, of which one, but optionally also two, contain a group of
the formula Va

Va

~, .

wherein R, X and X' have the meanings indicated above.
Components of this type are obtained by acylating the
corresponding components containing a group of the formula IIIa
,
-N-H
R IIIa

with a reactive triaYine derivative of the formula IV under
condltions which correspond to those described above for the
cor~esponding reaction of the dyestuff. The dyestuffs
obtained in this way are then reacted, in the manner described
above, with an amine of the formula IIa to give a dyestuff,
according to the invention, corresponding to the formula I.

~ Ref. 3062

1~37172
J
The amines of the formula IIa in which Z denotes a
~-halogenoethyl radical are manufactured by reacting an amine
which corresponds to the formula IIa and which contains a
chlorine atom instead of the -S02-Z group, with ~-hydroxyethyl-
mercaptan in an alkaline medium and subsequently oxidising the
resulting thioether with halogen, in solu~ion in a hydrogen
halide acid, according to the teachings of German Patent
887,505. Amines of the formula IIa in which Z denotes the
vinyl radical can be obtained by eliminating hydrogen chloride
from the amines Ila in which Z represents ~-halogenoethyl.
Dyestuffs, according to the invention, of the formula
I in which Z denotes vinyl can be obtained in an analogous
manner by elimination of hydrogen chloride, for example by
treatment with sodium bicarbonate in water at 50 - 60C, from
dyestuffs, according to the invention, of the formula I in
which Z represents ~-chloroethyl.
Reactive derivatives o~ the 1,3,5-triazine of the
formula IV are known. The following may be mentioned as
examples: trichlorotriazine, tribromotriazine, trifluoro-
triazine, trisulphotriazine, tris-methylsulphonyltriazine,
tris-ethylsulphonyltriazine, tris-phenylsulphonyltriazine,
diohlorofluorotriazine, chloro-disulphotriazine,and chloro-
bis-methylsulphonyltriazine.
The following are examples of amines of the formula
IIa. ~ -chloroethyl-sulphonyl)-ethyl-amine, ~ -bromoethyl-
sulphonyl)-ethyl-amine, ~-vinylsulphonyl-ethyl-amine, Y-(~-
chloroethyl-sulphonyl)-propyl-amine, ~ chloroethyl-sulphonyl)-
isopropyl-amine, ~ -chloroethyl-sulphonyl)-butyl-amine,

- 7 -




- .

. .

Ref. 3062
1~7~7Z


~ -chloroethyl-sulphonyl)-isobutyl-amine, -(~-chloroethyl-
sulphonyl)-pentyl-amine, ~ -chloroethyl-sulphonyl)-hexyl-
amine, N-methyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-
ethyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-propyl-N-
~ -chloroethyl-sulphonyl)-ethyl-amine, N-butyl-N-
~chloroethyl-sulphonyl)-ethyl-amine, N-pentyl-N-~ chloroethyl-
sulphonyl)-ethyl-amine, N-hexyl-N-~ chloroethyl-sulphonyl)-
ethyl-amine, N-nonyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine,
N-dodecyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-
hexadecyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-octa-
decyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-carboxy-
methyl-N-~ -bromoethyl-sulphonyl)-ethyl-amine, N-sulphato-
methyl-N~ -chloroethyl-sulphonyl)-ethyl-amine, N-~-carboxy-
ethyl-N-Y-(~-chloroethyl-sulphonyl)-propyl-amine, N-~-
sulphatoethyl-N-Y-(~-chloroethyl-sulphonyl)-propyl-amine,
N-~-sulphatoethyl-N-~ -chloroethyl-sulphonyl)-butyl-amine,
N-~-ethoxyethyl-N-~ -chloroethyl-sulphonyl)-butyl-amine,
N-Y-chloropropyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine,
N-phenyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine~ N-p-
chlorophenyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-o-
methylphenyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-p-
methoxyphenyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-m-

,
~: sulphophenyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-p-
sulphophenyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, bis-
-chloroethyl-sulphonyl)-ethyl]-amine, bis-[~ -bromo-
ethyl-sulphonyl)-ethyl]-amine, bis-~Y-(~-chloroethyl-sulphonyl)-
propyl]-amine, bis-~ -chloroethyl-sulphonyl)-butyl]-amine
and bis-(~-vinyl-sulphonyl-ethyl)-amine.

-- 8 --

--~ Ref. 3062
1~7~72


Amines of low-molecular weight, such as ~ -chloro-
ethyl-sulphonyl)-ethyl-amine and its N-methyl derivative, are
preferred. Bis-[~ -chloroethyl-sulphonyl)-ethyl]-amine
is particularly preferred.
In the dyestuffs of the formula III which are employed
for the manufacture of dyestuffs according to the invention,
F represents the radical of a water-soluble dyestuff which
carries at least 1 sulphonic acid group, especially the radi-
cal of a monoazo or disazo dyestuff which can be metal-free
or metallised, the radical of a derivative of l-amino-
anthraquinone or l-anilino-anthraquinone, especially the radi-
cal of a 4-phenylamino-1-amino-anthraquinone-2-sulphonic acid
derivative or the radical of a sulphophthalocyanine dyestuff,
especially a derivative, carrying at least two sulphonic acid
groups in the phthalocyanine nucleus, of a phthalocyanine-
sulphanilide or phthalocyanine-sulphalkylamide which has 2-6
C atoms in the alkyl chain, as well as the radicals of forma-
zan or nitroaryl dyestuffs.
An important group of dyestuffs of the formula III is
formed by those dyestuffs in which F is the radical of a mono-
azo or disazo dyestuff of the formula VIa or VIb

D-N=N-(M-N=N-)nK- or -D-N=N-(M-N=N-)nK
(VIa) (VIb)

or of a metal complex derived therefrom, in which formulae VIa
and VIb D represents the radical of a diazo component of
the benzene or naphthalene series which is optionally substi-
tuted by substituents customary in azo chemistry, especially

_ g _



.

;`~. Ref. 3062

; ~01~7~7Z


hydroxyl, methyl, ethyl, methoxy or ethoxy groups, optionally
substituted alkanoylamino groups having 2-4 C atoms, optionally
substituted benzoylamino groups or halogen atoms, K represents
the radical of a coupling component of the benzene,
naphthalene or ketomethylene series which is optionally sub-
stituted by substituents customary in azo chemistry, especially
hydroxyl, amino, methyl, ethyl, methoxy or ethoxy groups,
optionally substituted alkanoylamino groups having 2-4 C atoms,
optionally substituted benzoylamino groups or halogen atoms, M
represents the radical of a middle ~omponent o~ the benzene or
-naphthalene series which is optionally substituted by`substit-
-uents customary in azo chemistry, especially hydroxyl, methyl,
ethyl, methoxy or ethoxy groups, optionally substituted alkanoyl-
amino groups having 2-4 C atoms, optionally substituted benzcyl-
amino groups or halogen atoms, n represents the numbers 0 or
1 and D, M and K together contain at least two sulphonic
acid groups, preferably ~ to 4 sulphonic acid groups. K
is preferably derived from a coupling component of the benzene,
naphthalene, pyrazolone, 6-hydroxypyrid-2-one or acetoacetic
acid arylamlde series.
A further valuable group of dyestuffs o~ the formula
III in which p represents 2, contains as F the divalent radi-
cal of the ~ormula VIc
' -D-N=N-(M-N=N-)nK- VIc

wherein D, K, M and n have the abovementioned meanings, or a
metal complex derived therefrom.

-- 10 --

Ref. 3062

10~717Z

In the case where n = 0, the dyestuffs of the formula III
wherein F is a radical of one of the formulae VIa - VIc, can
be obtained in a manner which is in itself known by diazo-
tising suitable aromatic amines and coupling with suitable
coupling components, either the diazo component or the coup-
ling component or both containing a radical of the formula
-N-acyl or the coupling component containing a radical of the
R
ormula -N-H, and the acyl group being split off by saponifica-
R
tion after coupling.
In order to manufacture disazo dyestuffs of the formula
III, that is to say those dyestuffs in which F represents a
radical of one of the formulae VIa - VIc, n being 1, the dia-
zonium compound of a suitable aromatic amine is first coupled
with a suitable middle component.
In principle, middle components are all benzene or
naphthalene derivatives which contain an amino group which can
be diazotised.
The aminoazo compound which is then present is sub-
sequently diazotised and coupled with a suitable coupling
component, either the diazo component in the first coupling
or the coupling component in the second coupling or both con-
aining a radical of the formula -N-acyl, and the acyl group
R
being split off by saponification after coupling. The coup-

ling component can also contain a -NH group instead of the
R

-- 11 --

Ref. 3062
~717Z
:.


: -N-acyl group

: R
The aromatic amines which are given in List No. 1 which
follows are examples of amines which are suitable as diazo com-
ponents for the manufacture of dyestuffs of the formula IlI
. in which F is a radical of the formula VIa.
List 1:

Aniline; o-, m- or p-toluidine; o-, m- or p-anisidine;
.
o-, m- or p-chloroaniline; aniline-2-, -3- or -4-carboxylic
acid or aniline-2-, -3- or -4-sulphonic acid; aniline-2,4- or
-2,5-dicarboxylic acid or aniline-2,4- or -2,5-disulphonic
acid; 2-aminophenol-4-sulphonic acid; 2-aminophenol-4,6-
disulphonic acid; 4-chloro-2-aminophenol-5- or -6-sulphonic
acid; 6-chloro-2-aminophenol-4-sulphonic acid; 6-nitro-2-
aminophenol-4-sulphonic acid; 4-nitro-2-aminophenol-6-
sulphonic acid; 3- or 4-acetylamino-aniline-6-sulphonic acid;
3- or 4-benzoylamino-aniline-6-sulphonic acid; 4-amino-4'-
sulpho-benzanilide; 2-aminoanisole-4-sulphonic acid; 4-
aminoanisole-2- or -3-sulphonic acid; 3-aminoanisole-4-
sulphonic acid; 6-chloro-2-amino-benzene-sulphonic acid; 5-
nitro-2-amino-benzene-sulphonic acid; 4-chloro-3-amino-
benzene-sulphonic acid; 6-chloro-3-amino-benzene-sulphonic
acid; 3-chloro-4-amino-benzene-sulphonic acid; 2-amino-
toluene-4-sulphonic acid; 2-amino-toluene-5-sulphonic acid;
3-amino-toluene-6-sulphonic acid; 4-amino-toluene-2-sulphonic
acid; 4-amino-toluene-3-sulphonic acid; 5-chloro-2-amino-
toluene-3-sulphonic acid; 3-chloro-2-amino-toluene-5-sulphonic
acid; 2-chloro-4-amino-toluene-6-sulphonic acid; 3-nitro-2-
~ ' .

- 12 -

` ` Ref. 3062
1C~1371~72 ~ `
.;

amino-toluene-5-sulphonic acid; 3-nitro-4-amino-toluene-2-
sulphonic acid; 3-amino-1,2-dimethyl-benzene-4-sulphonic acid;
4-amino-1,3-dimethyl-benzene-5-sulphonic acid; 4-amino-1,3-
dimethyl-benzene-6-sulphonic acid; 4-chloro-2-amino-anisole-
5-sulphonic acid; 4-amino-phenetole-2-sulphonic acid; 4-
amino-phenetole-~-sulphonic acid; 2-amino-phenetole-4-
sulphonic acid; 2-amino-toluene-3,4-disulphonic acid; 2-
amino-toluene-3,5-disulphonic acid; 4-amino-2-sulpho-2'- or
-4'-methoxy-diphenylamine; 2-amino-diphenyl ether; 2-, 3-
or 4-aminobenzosulphamide; 2-naphthylamine-1-, -5-, -6-, -7-
or -8-sulphonic acid; 2-naphthylamine-1,5-, -1,7-, -3,6-,
-3,7-, -4,7-, -4,8-, -5,7- or -6,8-disulphonic acid; 2-
naphthylamine-1,5,7-, -3,6,8- or -4,6,8-trisulphonic acid;
l-naphthylamine-2-, -4-, -5-, -6- or -7-sulphonic acid; 1-
naphthylamine-3,6-, -3,7-, -3,8-, -4,6-, -4,7-, -4,8-, -5,7-
or -6,8-disulphonic acid; 1-naphthylamine-2,3,6-, -3,6,8- or
-4,6,8-trisulphonic acid; 2-amino-1-naphthol-4-sulphonic acid;
2-amino-1-naphthol-7-sulphonic acid; 1-amino-2-naphthol-4-
sulphonic acid; 4-nitro-2-amino-1-naphthol-7-sulphonic acid
,
and 5-nitro-1-amino-2-naphthol-4-sulphonic acid.
In the synthesis of dyestuffs of the formula III in
which F is a radical of the formula VIb or VIc, the diamines
which are given, for example, in List No. 2 are employed in
the form of their monoacyl derivatives.
Acyl groups which can be used are especially lower
alkanoyl groups having 1 to 5 C atoms, preferably formyl or
acetyl. As indicated above, the acyl grou~s are split off
after coupling, in order to obtain the dyestuffs of the formula




.

Ref. 3062

~08~7~7Z
.

III.
List 2:
p-Phenylenediamine; 1,4-phenylenediamine-2-sulphonic
acid; 1,4-phenylenediamine-2-carboxylic acid; 1,4-diamino-
naphthalene-2-sulphonic acid; 2,6-diamino-naphthalene-8-
sulphonic acid; 2,6-diamino-naphthalene-4,8-disulphonic acid;
1,6-diamino-naphthalene-4,8-disulphonic acid; m-phenylene-
diamine, 1,3-phenylenediamine-4-sulphonic acid; 1,3-phenylene-
diamine-4,6-disulphonic acid; 1,4-phenylenediamine-2,6-
disulphonic acid; 1,4-phenylenediamine-2,5-disulphonic acid;
1,4-diaminonaphthalene-6-sulphonic acid; 4,4~-diaminodiphenyl-
3-sulphonic acid and 4,4'-diaminostilbene-2,2'-disulphonic acid.
Examples of middle components which can be involved in
the synthesis of the radicals VIa to VIc are given in List No.
3 which ~ollows.
List No. 3:
Aniline; m-toluidine; 2,5-dimethyl-aniline or 2,5-
dimethoxy-aniline; m-amino-anisole; m-acetylamino-aniline,
m-propionylamino-aniline, m-butyrylamino-aniline or m-benzoyl-
amino-aniline; m-amino-phenylurea; 4-acetamino-2-amino-
toluene or 4-acetamino-2-amino-anisole; 2-amino-4-methyl-
anisole; 1-amino-naphthalene-6- or -7-sulphonic acid; 2-
amino-4-acetylamino-benzenesulphonic acid; 2-amino-5-naphthol-
7-sulphonic acid; 2-amino-8-naphthol-6-sulphonic acid; 2-(4-
aminobenzoyl-amino)-5-naphthol-7-sulphonic acid; 1-(4-amino-
2-sulphophenyl)-3-methyl-pyrazol-5-one or 1-(4-amino-2-
sulphophenyl)-3-carboxy-pyrazol-5-one; and acetoaceto-~-
sulpho-4-amino-anilide.

- 14 -

- ~ Ref. 3062
~1!3717~
'' . .

Examples of coupling components which are suitable for
the manufacture of dyestuffs of the general formula III wherein
F denotes a group of the formula VIb, are given in List No. 4
which follows.
List No. 4:
2-Naphthol; 2-naphthol-6-, -7- or -8-sulphonic acid;
2-naphthol-3,6-, -3,7-, -4,8- or -6,8-disulphonic acid;
2-napthol-3,6,8-trisulphonic acid; 1-naphthol-4-, -5-, -6-
or -8-sulphonic acid; 1-naphthol-3,6-, -3,7-, -3,8- or -4,8-
disulphonic acid; l-naphthol-3,6-, -3,7-, -3,8- or -4,8-
disulphonic acid; l-naphthol-3,6,8-trisulphonic acid; 2-
naphthylamine-5-, -6- or -7-sulphonic acid; 2-naphthylamine-
3,6-, -3,7-, -5 9 7- or -6,8-disulphonic acid; 1-amino-8-
naphthol-2,4-disulphonic acid; 2-ureido-5-naphthol-7-sulphonic
acid; 1-(4-sulphophenyl)-3-methyl-pyrazol-5-one or 1-(4-
sulphophenyl)-3-carboxy-pyrazol-5-one; 1-(4-methyl-2-
sulphophenyl)-3-methyl-pyrazol-5-one or 1-(4-methyl-2-sulpho-
phenyl)-3-carboxy-pyrazol-5-one; 1-(2,5-dichloro-4-sulpho-
phenyl)-3-methyl-pyrazol-5-one or 1-(2,5-dichloro-4-sulpho-
phenyl)-3-carboxy-pyrazol-5-one; 4-acetoacetylamino-benzene-
sulphonic acid; 4-acetoacetylamino-3,6-dimethoxy-benzene-
sulphonic acid; barbituric acid and 6-hydroxy-4-methyl-3-
sulpho-pyrid-2-one or 6-hydroxy-4-methyl-3-carbonamido-pyrid-
2-one.
Examples of coupling components which are suitable for
the synthesis of dyestuffs of the formula III wherein F is a
gr ~ of the formula VIa or VIc, are given in List No, 5 which
follo~s.




- 15 -

Ref. 3062
; ~0~3717Z


List No. 5:
Aniline; m-toluidine; 2,5-dimethyl-aniline or 2,5-
dimethoxy-aniline; m-amino-anisole; m-acetylamino-aniline,
m-propionylamino-aniline, m-butyrylamino-aniline or m-benzoyl-
amino-aniline; m-amino-phenylurea; 4-acetamino-2-amino-
toluene or 4-acetamino-2-amino-anisole; 2-amino-4-methyl-
anisole; 1-amino-naphthalene-6-, -7- or -8-sulphonic acid;
2-amino-4-acetylamino-benzenesulphonic acid; 2-amino-5-
naphthol-7-sulphonic acid; 2-amino-8-naphthol-6-sulphonlc
acid; 2-(4-aminobenzoyl-amino)-5-naphthol-7-sulphonic acid;
1-(4-amino- or 4-acetylamino)-2-sulphophenyl)-3-methyl-pyrazol-
5-one or 1-(4-amino- or 4-acetylamino)-2-sulphophenyl)-3-
carboxy-pyrazol-5-one; acetoaceto-3-sulpho-4-amino-anilide;
l-amino-8-naphthol-3,6- or 4,6-disulphonic acid; 1-(3- or 4-
aminobenzoyl)-amino-8-naphthol-3,6- or -4,6-disulphonic acid;
l-acetylamino-8-naphthol-3,6- or -4,6-disulphonic acid; 2- .
acetylamino-5-naphthol-7-sulphonic acid; 2-acetylamino-8-

.
naphthol-6-sulphonic acid; 1-(3-amino or 3-acetylamino-6-
sulphophenyl)-3-methyl- or -3-carboxy-pyrazol-5-one; 2-
acetyl-methylamino or 2-methylamino-5-naphthol-7-sulphonic
acid; N-methylaniline and N-propyl-m-toluidine,
Disazo dyestuffs which carry one or two -NH or
R-.
-N-acyl groups and which are suitable for the manufacture of
R
reactive dyestuffs .according to the invention can also be
obtained by tetrazotising an aromatic diamine which containstwo
primary amino groups and coupling the tetrazo compound thus

- 16 -

Ref. 3062
10 !37~72

obtained with 2 molar fractions of a coupling component which
contains a -NH or -N-acyl group, for example one of those indi-
R R
cated in List 5, or with 1 molar fraction of each of two
different coupling components of this type or with 1 molar
fraction of a coupling component of this type and with 1 molar :
fraction of a coupling component which does not contain a
-NH or -N-acyl group, for example one of those indicated in
R R
List 4, The following may be mentioned as examples of such
i~ - aromatic diamines:
List No. 6:
3,3'-Dimethoxybenzidine, benzidine-2,2'-disulphonic
acid, benzidine-3,3'-dicarboxylic acid, benzidine-3,3'-
diglycollic acid and 4,4'-diaminostilbene-2,2'-disulphonic
acid.
Further disazo dyestuffs which carry one or two -NH

groups and which are suitable for the manufacture of reactive
dyestuffs according to the invention can be obt8ined by coupling
~ ~ either 2 molar fract~ns of a diazotised amine which carries a
:: -N-acyl group, for example an acyl derivative of one of the

: ~ amines in List 2, or 1 molar fraction of one of these diazo-
tised amines and 1 molar fraction of a diazotised amine which
does not carry a -N-acyl group, for example one of the amines
~ R
~ in List 1, with a coupling component which can undergo couplingin two places, and subsequently saponifying the resulting

Ref. 3062
7~72

.

dyestuffs. If 2 molar fractions of the amines which carry
a -N-acyl group are used, 2 molar fractions of the same amine
R
or 1 molar fraction of each of two different amines can be
employed,
Examples of suitable coupling components which can
undergo coupling in two places are l-amino-8-naphthol-3,6-
or 4,6-disulphonic acid, resorcinol or 5,5'-dihydroxy-7,7'-
disulpho-2,2'-dinaphthylurea.
The dyestuffs of the formula III can be obtained in
complete analogy with the possible manufacturing methods des-
cribed above if, instead of the diazo components or coupling
components indicated in Lists 2, 3 and 5, compounds are
employed which contain a nitro group instead of the -NH or
R
-N-acyl group and if the nitro group of the azo compounds syn-


theslsed from these components is reduced to give the aminogroup. The conditions for this reduction are in themselves
known. A reducing agent which is known for this purpose is
alkali metal sulphide, which reduces the nitro group in an
aqueous medium at temperatures of 40 to 70 without attacking
the azo group.
Exa~ples of the radicals F of particularly valuable
mono~zo and disazo dyestuffs which are suitable for the manu-
facture of dyestuffs according to the invention, are shown by
means of the following formulae, wherein the benzene and naphtha-
lene nuclei can be substituted in accordance with the

- 18 -

" Ref. 3062
10871~2
.

illustrations given for D, M and K and the position of the
radical of the formula IIIa is indicated by means of the open
bond: . -

0~1
N - N


0
N - N



N - N ~


OIH . .
- N - N

~ ,
0
N - N ~ H C


~
r,'; ~ N - N ~ 8 O



-- 19 --



.


`- Ref, 3062

'10~7~
o~
-CEI2 ~N - N~

.

,~ N - ~b(CH3 or C00~)


' '. .

,~ N ~(CEI~ Oa~)




~N -- N~

.' , .
~N - N~ N - N~


.
Me ~
O
N -- N ~ X~


-- 20 --




~ .

~0~7~72 Ref. 3062



~e
O~ ~ O
N -- N


Me
~0/ \0 ' `
_$N - N ~
;, .
'.:


Me

~N ~ N ~N - N ~



: ~ O ~ -- ' `"

~3-11 - N ~N - N ~


:~ ' 0 ~ ~ O
~ N ~ N - N r ~




-- 21 --




.

~ Ref, 3062
~ot37~7Z


The following are examples of diazo components from
which particularly valuable monoazo dyestuffs of the formula
III can be manufactured: aniline-2-sulphonic acid; aniline-
2,5-disulphonic acid; 2-naphthylamine-1-sulphonic acid; 2-
naphthylamine-1,5-disulphonic acid; 2-naphthylamine-4,8-
disulphonic acid; 2-naphthylamine-3,6,8-trisulphonic acid;
and 2-naphthylamine-4,6,8-trisulphonic acid.
The following are examples of coupling components from
which particularly valuable monoazo dyestuffs can be manufactured:
1-amino-8-naphthol - 3,6-disulphonic acid; 1-amino-8-naphthol-
4,6-disulphonic acid; 2-amino-5-naphthol-7-sulphonic acid;
1-(4-amino-2-sulphophenyl)-3-carboxy-pyrazolone; 1-(5-amino-
2-sulphophenyl)-3-carboxy-pyrazol-5-one; aniline; N-methyl-
aniline; 3-amino-toluene; 3-amino-acetanilide and 3-amino-
phenylurea.
The followlng are examples of particularly valuable
monoazo dyestuffs of the formula III:

0~ N~2
D~ - N; ~


wherein Dl is the 2-sulphophenyl radlcal, the 1-sulpho-2-
naphthyl radical or the l,5-disulpho-2-naphthyl radical and
the coupling component is substituted by a further sulphonic
acid group in the 3- or 4-position.
.




- 22 -

r-- .
Re~. 3062
10~37~72


o~
D2 ~ N - N ~ ~
H03~H

, , .
wherein D2 is the 2-sulphophenyl radical, the 2,5-disulpho-
phenyl or the 1,5-disulpho-2-naphthyl radical, the coupling
component carries no further substituents and R2 represents
hydrogen or methyl.

3 ~ ~
H0 ~ S03H

- ~ N

wherein D3 is the 2-sulphophenyl radical or the 1-sulpho-2-
naphthyl radical and the amino group in the 2-sulphophenyl
i. ,~ , .
~ nucleus of the coupling component is in the 4- or 5-position.

.; ~
~ N - N ~ - ~

j~ wherein D4 is the 2,5-disulphophenyl radical, the 4,8-disulpho-
2-naphthyl radical, the 3,6,8-trisulpho-2-naphthyl radical or
the 4,6,8-trisulpho-2-naphthyl radical, the coupling component
canlbe substituted in the o-position-relative to the azo group
by a methyl group, an acetamino group or the urea radical,
~ .
and R2 represents hydrogen or methyl.
The following are examples of individual dyestuffs of

- 23 -




.


. ~- Ref. 3062

; ~0~717Z

the formula III in which F is a radical of a monoazo or
disazo dyestu~f: 1-(3'-aminobenzoylamino)-8-hydroxy-7-(2'-
sulphophenylazo)-naphthalene-3,6-disulphonic acid, 1-(4'-
aminobenzoylamino)-8-hydroxy-7,2'-azonaphthalene-1',3,5',6-
tetrasulphonic acid, l-amino-8-hydroxy-7,2'-azonaphthalene-
1',4,6-trisulphonic.acid, l-(.aminoacetylamino)-8-hydroxy-7,2'-
azonaphthalene-1'~3,5',6-tetrasulphonic acid, 2-methylamino-
5-hydroxy-6,2'-azonaphthalene-1',5',7-trisulphonic acid,
2-amino-8-hydroxy-7,2'-azonaphthalene-1',6-disulphonic acid,
2-methylamino-8-hydroxy-7,2'-azonaphthalene-1',6,5'-trisulphonic
acid, 2-amino-5-hydroxy-6-(2',5'-disulphophenylazo)-naphthalene-
7-sulphonic acid, 2-methylamino-5-hydroxy-6-(4'-methoxy-2'-
sulphophenylazo)-naphthalene-7-sulphonic acid, 1-amino-8-
hydroxy-7-(2'-sulphophenylazo)-naphthalene-3,6-disulphonic acid,
l-amino-8-hydroxy-7-(4'-chloro-2'-sulphophenylazo)-naphthalene-
4,6-disulphonic acid, 2-(4'-amino-2'-methylphenylazo)-
naphthalene-4,8-disulphonic acid, 2-(4'-amino-2'-methylphenyl-
azo)-naphthalene-4,6,8-trisulphonic acid, 2-(4l-amino-2'-
acetylaminophenylazo)-naphthalene-5,7-disulphonic acid, 2-(4'-
amino-2'-acetylaminophenylazo)-naphthalene-3,6,8-trisulphonic
acid, 4-nitro-4'-(4"-methylaminophenylazo)-stilbene-2,2'-
disulphonic acid, 4-nitro-4'-(4"-amino-2"-methyl-5"-methoxy-
phenylazo)-stilbene-2,2'-disulphonic acid, 1-(2',5'-dichloro-
4'-sulphophenyl)-3-methyl-4-(3"-amino-6"-sulphophenylazo)-5-
pyrazolone, l-(4'-sulphophenyl)-3-carboxy-4-(4~'-amino-2"-
sulphophenylazo)-5-pyrazolone, l-(2'-methylphenyl)-3-methyl-
4-(4"-amino-2",5"-disulphophenylazo)-5-pyrazolone, l-(2'-
sulphophenyl)-3-methyl-4-(3"-amino-6"-sulphophenylazo)-5-


- 24 -




..
,

- Ref. 3062
7~7z

pyrazolone, 2-(3'-sulphophenylamino)-5-hydroxy-6-(4'-amino-
2'-sulphophenylazo)-naphthalene-7-sulphonic acid, 1-(3'-
aminophenyl)-3-methyl-4-(2",5"-disulphophenylazo)-5-pyrazolone,
l-(3'-amino-6'-sulphophenyl)-3-carboxy-4-(2'-sulphophenylazo)-
5-pyrazolone, I-(4'-amino-2'-sulphophenyl-3-carboxy-4-(2'-
sulphophenylazo)-5-pyrazolone, l-(4'-amino-2'-sulphophenyl)-
3-carboxy-4-[4"-(2"',5"'-disulphophenylazo)-2"-methoxy-5"-
methylphenylazo]-5-pyrazolone, the copper complex of l-amino-
8-hydroxy-7-(2'-hydroxy-5'-sulphophenylazo)-napthalene-3,6-
disulphonic acid, the copper complex of 2-amino-5-hydroxy-6-
(2'-hydroxy-3'-sulpho-5'-nitrophenylazo)-naphthalene-7-
sulphonic acid, the copper complex of 2-amino-5-hydroxy-6-
(2'-hydroxy-5'-sulphophenylazo)-naphthalene-1,7-disulphonic
acid, the copper complex of l-amino-8-hydroxy-7-(2'-hydroxy-
3'-chloro-5'-sulphophenylazo)-napthalene-3,6-disulphonic acid,
the copper complex of 2-methylamino-5-hydroxy-6-(2'-carboxy-
5'-sulphophenylazo)-naphthalene-7-sulphonic acid, 4,4'-bis-
(l"-amino-8"-hydroxy-3",6"-disulpho-7"-naphthylazo)-3,3'-
dimethoxydiphenyl, 2-amino-5-hydroxy-6-[4'-(2"-sulphophenyl-
azo)-2'-methoxy-5'-methylphenylazo]-naphthalene-1,7-disulphonic
acid, l-amino-8-hydroxy-2-(2',5'-disulphophenylazo)-7-(3'-
amino-6'-sulphophenylazo)-naph*halene-3,6-disulphonic acid,
the copper complex of l-amino-8-hydroxy-7-[4'-(2"-sulphophenyl-
azo)-2'-hydroxy-5'-methylphenylazo]-naphthalene-3,6-disulphonic
acid, the copper complex of 2-amino-5-hydroxy-6-[4'-(2",5"-
disulphophenylazo)-2'-hydroxy-5'-methylphenylazo]-naphthalene-
7-sulphonic acid, the copper complex of 1-(4'-amino-2'-
sulphophenyl)-3-carboxy-4-[4"-(2"',5"'-disulphophenylazo)-2"-

-- 25 --




.

~ . Ref. 3062
; 1~871q2


hydroxy-5"-methylphenylazo]-5-pyrazolone, the copper complex
of 2-(4'-amino-3'-sulphoanilino)-5-hydroxy-6-(2"-carboxyphenyl-
azo)-naphthalene-7-sulphonic acid, the 2:1 chromium complex of
2-amino-6'-nitro-8,2'-dihydroxy-7,1'-azonaphthalene-6,4'-
disulphonic acid, the 2:1 chromium complex of 2-amino-5-
hydroxy-6-(2'-carboxyphenylazo)-naphthalene-7-sulphonic acid,
the 2:1 chromium complex of 1-amino-8-hydroxy-7-(4'-nitro-2'-
hydroxyphenylazo)-naphthalene-3,6-disulphonic acid, the 2:1
cobalt complex of 2-(4'-amino-3'-sulphoanilino)-5-hydroxy-6-
(5"-chloro-2"-hydroxyphenylazo)-naphthalene-7-sulphonic acid,
the copper complex of 2-amino-6'-nitro-2',8-dihydroxy-1',7-
azonaphthalene-4',6-disulphonic acid, the copper complex of
; 1,6'-diamino-2',8-dihydroxy-1',7-azonaphthalene-2,4,4'-
trisulphonic acid, the copper complex of 6'-amino-1',2-
dihydroxy-1,2'-azonaphthalene-3,4',6,8'-tetrasulphonic acid
and the copper complex of l-amino-1',8-dihydroxy-2',7-azo-
naphthalene-3,4',6,8'-tetrasulphonic acid.
: A further means of manufacturing dyestuffs according
to the invention consists in manufacturing monoazo or disazo
dyestuffs or optionally metal complexes thereof of the formula
V
r~N ~ X ' ~ (V)

y P
wherein F is a radical of one of the formulae VIa to VIc indi-
cated above and X and X' have the meanings indicated above,
direct by using diazo components and coupling components, one

- 26 -




.

. Ref. 3062
~a7l7z


of which, but also, if appropriate, both of which, contain a
group of the formula Va

-N ~ X'
R ~ (Va)
X
and then reacting them with an amine of the formula IIa, as
: described above.
The starting materials required for this purpose are
obtainèd by reacting diazo components or coupling components
which contain a radical of the formula -NH, with acylating

agents of the formula IV.
: Diazo components for the direct manufacture of azo
dyestuffs of the formula V in which F is a radical of the form-
` ula VIb or VIc can be obtained, for example, by acylating the
-NH group in an aromatic amine indicated in List 2 with an acyl-
: R
ating agent of the formula IV.
Coupling components for the direct manufacture of azo
dyestuffs of the formula V in which F is a radical of the form-
ula VIa or VIc can be obtained, for example, by acylating the
-NH group of a coupling component mentioned in List 5 with an
: R
acylating agent of the formula IV.
Chromium, manganese, cobalt, nickel and copper are
examples Gf complex-forming metals which can be present in
radicals of metal-containing monoazo or disazo dyestuffs which

- 27 -

` Ref, 3062
~ 7~72
.

represent F. Copper, chromium and cobalt are preferred.
A further important group of dyestuffs of the general
formula III is formed by those dyestuffs in which F is the
radical of a derivative of l-amino-anthraquinone or l-anilino-
anthraquinone, especially the radical of a 4-phenylamino-1-
amino-anthraquinone-2-sulphonic acid derivative. Suitable
aminoanthraquinones contain 2 to 3, preferably 2, amino groups,
which can also be substituted by alkyl or aryl.
Alkyl radicals have, in particular, 1 to 4, preferably
1-2, C atoms; phenyl is preferred as an aryl radical. The
derivatives of the aminoanthraquinone can contain 1 or 2 sul-
phonic acid groups directly in the anthraquinone nucleus and
one or two sulphonic acid groups in aromatic substituents which
may be present in the anthraquinone nucleus. The group

~, ~ . .
:~' X
can be directly linked to the anthraquinone nucleus, but is
preferably linked to a substituent in the anthraquinone nuc-
leus.
In a preferred group of anthraquinone dyestuffs, accor-
ding to the invention, of the formula I, F represents a radical
of the formula VII




- 28 -




. :

10 8 7 1 ~ Ref. 3062
.; .


~p NII2

(VII)
0 N-Z-
H
in which the anthraquinone nucleus can be substituted by a
further sulphonic acid group. Z represents a phenyl radical
which carries a radical of the general formula IIIa. The
phenyl radical Z can be substituted by a sulphonic acid group
or a carboxylic acid group, so that the dyestuff contains at
least two groups which strongly impart solubility in water.
Furthermore, the phenyl radical can be substituted by an alk-

. ~, ~ , ,
oxy group having 1-3 C atoms, by a halogen atom or by 1-3
; alkyl groups having 1-3 C atoms.
The preferred anthraquinone dyestuffs of the general
formula III in which F is a radical of the formula VII, are
manufactured by a condensation reaction between a diamine of
,
the general formula H2N-Z-N-H or its monoacyl derivative
R
H2N-Z-N-acyl and an anthraquinone derivative which contains a

reactive s~bstituent, for example a Br atom, in the 4-position.
In this context, acyl has the meanings indicated above, par-
ticularly the meanings which are characterised as pre~erred.
. .
The following are examples of suitable diamines of the
formula H2N-Z-N-H, which can also be employed in the form of
R
their acyl derivatives: 2,4-diaminobenzenesulphonic acid,
~ ~ 2,4-diaminotoluene-6-sulphonic acid, 2,6-diaminotoluene-4-
::
- 29 -




......

~ Ref. 3062
l~)B7172


sulphonic acid, 3,5-diaminobenzenesulphonic acid, 2,4,6-tri-
methylbenzenesulphonic acid, p-phenylenediamine, 2,5-diamino-
benzenecarboxylic acid, 2,5-diaminobenzenesulphonic acid and
2,4-diaminobenzenecarboxylic acid.
The following are examples of dyestuffs of the formula
III in which F is the radical of a l-amino-anthraquinone: 1-
amino-4-(3'-amino-4'-sulphoanilino)-anthraquinone-2-sulphonic
acid, l-amino-4-(3-amino-2',4',6'-trimethyl-4'-sulphoanilino)- ~ -
~nthraquinone-2-sulphonic acid, 1-amino-4-(4'-amlno-3'-
sulphoanilino)-anthraquinone-2,5-disulphonic acid and l-amino-
5,8-bis-(4'-methyl-2'-sulphoanilino)-anthraquinone. :
A further important group of dyestuffs of the general
formula III is formed by those dyestuffs in which F represents
the radical of a sulphophthalocyanine dyestuff, especially a
derivative of phthalocyaninesulphanilide or phthalocyaninesulph-
alkylamide which has 2-6 C atoms in the alkyl chain and which
carries at least 2 sulphonic acid groups in the phthalocyanine
nucleus.
A preferred group of phthalocyanine dyestuffs of the
general formula III is formed by those dyestuffs in which F
represents a radical of the formula VIII

( S3W)k
(Sa N B )P


wherein PG denotes the radical of a metal-containing or metal-
free phthalocyanine nucleus, preferably of copper phthalo-
cyanine or nickel phthalocyanine, W denotes -OH and/or -NR'R"

- 30 -




~.
.

~717Z Re~. 3062

wherein R' and R" independently oi one another represent hydro-
gen or alkyl having 1-4 C atoms, k denotes the numbers 2 or 3,
p denotes the numbers 1 or 2 and B denotes a phenyl radical
which is optionally ~ubstituted by halogen, 1-3 alkyl groups
havlng 1-2 C atoms or by one or two sulphonic acid groups or
carboxylic acid groups or denotes an alkyl radical having 2-6
C atoms.
~ A phenyl radical which is substituted by I sulphonic
; acid group is preierred, as 1-~ the ethylene radical.
The dyestuii's oi the iormula III in whlch F represents
a radical oi the iormula VIII are manu~actured in a manner
which is in itselr known by a condensation reaction between a
sulphochloride oi the iormula :~

~(S03W)k
Pc
\ ~ ) .
p
~: whereln Pc, W,k and p have the meanings indicated above, and a
: diamine oi the general iormula HN-B-NH or its monoacyl deriva-
` R R
: tive HN-B-N-acyl wherein acyl has the abovementloned meanings,
R' R
: particularly the meaning~ characterised as preferred, The
iollowing are examples o~ diamines oi' the ~ormula HN-B-N~ which
Rt R
are suitable ior the manufacture oi the preierred phthalo-
cyanine dyestuiis oi' the iormula III: m-phenylenediamine, p-
phenylenediamine, 2,4-diaminobenzenesulphonic acid, 2,5-
diaminobenzene~ulphonic acid, 2,5-diaminobenzenecarboxylic
: acid, 2,5-diaminobenzene-1,4-disulphonic acid, 2,4-diamino-




-31-

~8717Z Ref. 3062



toluene-6-sulphonic acid, ethylenediamine and hexamethylene-
diamine.
The following are examples of dyestuffs of the formula
III in which F is the radical of a N-substituted phthalocyanine-
sulphonamide: 3-[N-(3-amino-4-sulphophenyl)-sulphamyl]-copper-
phthalocyanine-3',3",3"'-trisulphonic acid, bis-4,4'-rN-3-
amino-4-sulphophenyl)-sulphamyl]-copper-phthalocyanine-4",4"'-
disulphonic acid, 3-[N-(4-amino-3-sulphophenyl)-sulphamyl]-
nickel-phthalocyanine-3',3",3"'-trisulphonic acid, 3-rN-(3-
aminophenyl)-sulphamyl]-31-sulphamyl-copper-phthalocyanine-311,3"'-
disulphonic acid and 3-(N-~-aminoethyl-sulphamyl)-copper-
phthalocyanine-3',3",3"'-trisulphonic acid.
The reactive dyestuffs, according to the invention,
of the formula I are outstandingly suitable for dyeing and
printing cellulose and cellulose-containing materials. They
are distinguished particularly in printing processes by a uni-
formly high degree of fixing, independently of the nature of
the fixing, for example in fixing by steaming or dry heat or
by a one-phase or two-phase process. Very good results are
also obtained in the various dyeing processes, for example in
the exhaustion process or the pad-batch process or the pad-
thermofix process. The dyeings and prints obtained have a
high brilliance and depth of colour together with very good
fastness to light, even in a wet condition, very good fastness
to wet processing, such as washing at 60 and at 95, and
good fastness inuse, such as fastness to sea water, fastness
to acid and alkaline perspiration, fastness to chlorinated pool

-- 32 --

~7~7~ Ref. 3062



water, fastness to peroxides and fastness to flue gas. The
dyestuffs are also distinguished by insensitivity towards
atmospheric influences.
Very good results are also obtained when they are used
on polyamides, especially wool, in reactive dyeing processes.
Besides very good fastness to light, the outstanding fastness
to washing and perspiration should be singled out particularly,
as well as their excellent build-up capacity.
The temperatures quoted in the examples which follow
relate to C, parts are parts by weight and percentages are
percentages by weight.
ExamPle 1:
.
18.5 parts of cyanuric chloride are dissolved in 110
parts of acetone and the mixture is poured onto 250 parts of
ice, while stirring vigorously. A solution of 55.3 parts
of the dyestuff of the following structure
: :
03H 0~ N~2
N - N ~ ~
H03S ~ S03H
3~
is run in at 0. 50 parts of 2 normal sodium carbonate
solution are then added dropwise, a pH value of 6-6.5 resul-
ting. 36.3 parts of bis-[~ -chloroethyl-sulphonyl)-ethyl]-
amine hydrochloride are now added in the form of a powder.
The mixture is warmed to 40 in the course of ~ hour and this
~- temperature is maintained for 3 hours. At the same time,

- 33 -

~ Ref. 3062
1087~72


100 parts of 2 normal sodium carbonate solution are added drop-
wise at a pH value of 4.0-4.5. 25% strength potassium
chloride is added in order to make the product separate out
and the mixture is cooled to 20-25 whilst stirring and is
filtered. About 235 parts of a dyestuff paste are obtained,
which is dried at 60-65 in vacuo. The reactive dyestuff
prepared has the following structure:

~ " ~ N(c~I2cH2so2cH2cH2ci~2

N - ~ H Cl

The dyestuff employed above, l-amino-8-hydroxy-2',7-
azo - naphthalene-1',3,5',6-tetrasulphonic acid, can be
obtained as follows: 60.6 parts of 2-naphthylamine-1,5-
disulphonic acid are dissolved in 300 parts of water and about
20 ml of 10 normal sodium hydroxide solution by warming to 60
at pH 7 - 8. A solution of 14 parts of sodium nitrite in
60 parts of water is added thereto. This mixture, warmed
to 60, is run into a mixture of 50 parts of 10 normal hydro-
chloric acid and 500 parts of ice, the intention being to
maintain a temperature of 0 - 5 during the diazotisation.
Stirring is continued for ~ hour and the excess of ni~trous
acid which is present is destroyed by adding aminosulphonic
acid. The diazo compound separates out as a pale yel-
lowish precipitate. This suspension is run, at 0 - 5,
into 72.2 parts of 1-acetamino-8-naphthol-3~6-disulphonic acid,
dissolved to form a neutral solution in 500 parts of water,

- 34 -




: . .' .,; '

Ref, 3062
717Z


200 parts of ice and 17 parts of sodium bicarbonate. The
coupling is completed at a pH value of 7. After adding 60
parts of 10 normal sodium hydroxide solution, the mixture is
heated at 70 for 3 hours, as a result of which the acetyl
group is saponified. lO~o strength potassium chloride and
15% strength sodium chloride are added to the dyestuff solu-
tion to make the saponified dyestuff separate out, the mixture
is neutralised with 22 parts of 10 normal hydrochloric acid,
cooled to 20 - 25 and filtered and the product is washed with
600 parts of sodium chloride solution (density 1.142),
Equally valuable dyestuffs according to the invention are
obtained if the 2-naphthylamine-1,5-disulphonic acid is
replaced by molar quantities of one of the diazo components
mentioned in the following text and if the procedure is in
other respects as described: 3-amino-benzene-sulphonic acid,
4-amino-benzene-sulphonic acid, 5-chloro-2-amino-benzene-
sulphonic acid, 6-chloro-2-amino-benzene-sulphonic acid, 5-
nitro-2-amino-benzene-sulphonic acid, 4-chloro-3-amino-benzene-
sulphonic acid, 6-chloro-3-amino-benzene-sulphonic acid, 3-
chloro-4-amino-benzene-sulphonic acid, 2-amino-toluene-4-
sulphonic acid, 2-amino-toluene-5-sulphonic acid, 3-amino-
toluene-6-sulphonic acid, 4-amino-toluene-2-sulphonic acid,
4-amino-toluene-3-sulphonic acid, 5-chloro-2-amino-toluene-3-
sulphonic acid, 3-chloro-2-amino-toluene-5-sulphonic acid, 6-
chloro-3-amino-toluene-4-sulphonic acid, 2-chloro-4-amino-
toluene-5-sulphonic acid, 2-chloro-4-amino-toluene-6-sulphonic
acid, 4-nitro-2-amino-toluene-6-sulphonic acid, 6-nitro-4-amino-
toluene-2-sulphonic acid, 3-amino-1,2-dimethyl-benzene-4-


- 35 -

1~7~72 Ref. 3062
.; '


sulphonic acid, 4-amino-1,3-dimethyl-benzene-5-sulphonic acid, ~
4-amino-1,3-dimethyl-benzene-6-sulphonic acid, 2-amino-anisole- -
4-sulphonic acid, 4-amino-anisole-2-sulphonic acid, 4-amino-
anisole-3-sulphonic acid, 4-chloro-2-amino-anisole-5-sulphonic
acid, 4-amino-phenetole-2-sulphonic acid, 4-amino-phenetole-3-
sulphonic acid, 2-amino-phenetole-4-sulphonic acid, 4-amino-
benzene-1,3-disulphonic acid, 2-amino-benzene-1,4-disulphonic
acid, 2-amino-toluene-3,4-disulphonic acid, 2-amino-toluene-
3,5-disulphonic acid, aniline, 4-amino-toluene, 4-amino-
anisole, 4-amino-chlorobenzene, 2-aminobenzene-sulphonic acid,
2-naphthylamine-1-sulphonic acid, 2-naphthylamine-5-sulphonic
acid, 2-naphthylamine-6-sulphonic acid, 2-naphthylamine-7-
sulphonic acid, 2-naphthylamine-8-sulphonic acid, 2-naphthyl-
amine-1,7-disulphonic acid, 2-naphthylamine-3,6-disulphonic
acid, 2-naphthylamine-3,7-disulphonic acid, 2-naphthylamine-
4,7-disulphonic acid, 2-naphthylamine-4,8-disulphonic acid,
2-naphthylamine-5,7-disulphonic acid, 2-naphthylamine-6,8-
disulphonic acid, 2-naphthylamine-1,5,7-trisulphonic acid, 2- . .
naphthylamine-3,6,8-trisulphonic acid, 2-naphthylamine-4,6,8-
:~ trisulphonic acid, l-naphthylamine-4-sulphonic acid, 1-
naphthylamine-5-sulphonic acid, 1-naphthylamine-6-sulphonic
acid, l-naphthylamine-7-sulphonic acid, 1-naphthylamine-3,6-
disulphonic acid, l-naphthylamine-3,7-disulphonic acid, 1-
naphthylamine-3,8-disulphonic acid, 1-naphthylamine-4,6-
disulphonic acid, l-naphthylamine-4,7-disulphonic acid, 1-
naphthylamine-4,8-disulphonic acid, 1-naphthylamine-5,7-
disulphonic acid, l-naphthylamine-6,8-disulphonic acid, 1-

- 36 _




. . - ' : . ~ : .
.

Ref. 3062
108717Z


naphthylamine-2,4,6-trisulphonic acid, 1-naphthylamine-3,6,8-
trisulphonic acid and l-naphthylamine-4,6,8-trisulphonic acid.
Equally valuable dyestuffs according to the invention
are obtained if the l-acetamino-8-naphthol-3,6-disulphonic
acid employed as the coupling component for the preparation
of the starting dyestuff is replaced by molar quantities of
the acetyl compound of one of the coupling components men-
tioned in the following text and if the procedure is in other
respects as described above: 1-amino-8-naphthol-4,6-disul-
phonic acid, 2-amino-8-naphthol-6-sulphonic acid, 2-methyl-
amino-8-naphthol-6-sulphonic acid, 2-carboxymethylamino-8-
naphthol-6-sulphonic acid, 2-~-sulphoethylamino-8-naphthol-6-
sulphonic acid, 2-iso-propylamino-8-naphthol-6-sulphonic acid,
2-amino-5-naphthol-7-sulphonic acid, 2-methylamino-5-naphthol-
7-sulphonic acid, 2-ethylamino-5-naphthol-7-sulphonic acid,
2-n-butylamino-5-naphthol-7-sulphonic acid, 1-amino-8-naphthol-
4-sulphonic acid, 2-amino-8-naphthol-4-sulphonic acid and 2-
amino-8-naphthol-3,6-disulphonic acid.
Preparation of bis-[~ -chloroethylsulphonyl)-ethyl]-
amine: 156 parts of ~-hydroxyethylmercaptan, followed by 178.5
parts of bis-(~-chloroethyl)-amine hydrochloride (J, Chem.
Soc. 1934, 464), are added to-a solution of 69 parts of sodium
in 1,200 parts by volume of ethyl alcohol, the temperature
rising to 40 - 50. The mixture is then warmed for 1 hour
at 78 and cooled and the sodium chloride which has precipi-
tated is filtered off and the ethyl alcohol is distilled off.
The residue is taken up in 1,000 parts by volume of water and
the pH is adjusted to 3 with approximately 90 parts by volume

- 37 -

Ref. 3062
; ~0~71~72


of 37% strength hydrochloric acid. 295 parts of chlorine
are then passed in during 90 minutes. The hydrochloride
which is precipitated is filtered off and washed with ice
water. It can be recrystallised from water. Melting
point 205.
Analysis:
calculated: C 26.5%; H 5.0%; Cl 29,3%; N 3.9%; S 17.7%
found: C 26.6%; H 5.2yo; Cl 29.3%; N 4.1%; S 18.3%
If the hydrochloride is stirred with sulphuric acid at
room temperature and the product is precipitated by pouring
onto ice, the neutral sulphate is obtained. Melting point
150 - 152.
Analysis:
calculated: Cl 18.9~; N 3.7%; S04 12.8%
found: Cl 18.9%; N 3.8%; S04 13.0%
Exam~le 2:
.
~ 42.3 parts of the dyestuff 2-amino-5-hydroxy-6-(2-
.
sulphophenylazo)-naphthalene-7-sulphonic acid are reacted with
18.5 parts of cyanuric chloride and 36.3 parts of bis-(~-
chloroethyl-sulphonyl-ethyl)-amine hydrochloride as described
in Example 1. 20% strength sodium chloride and 10% strength
potassium chloride are added to the neutral solution to make
the dyestuff separate out and the mixture is filtered. me
resulting paste is dried in vacuo at 50 - 70. The reac-
tive dyestuff prepared in this way has the following structure:




- 38 -



' , ~

~~ Ref, 3062
10~7172



. . .
803H ~ Cl
N-N ~ ~
(C~2C~2S02C~2c~2cl)2

The starting dyestuff 2-amino-5-hydroxy-6-~2-sulphophenylazo)-
naphthalene-7-sulphonic acid which is required for the prepara-
tion of the dyestuff according to the invention can be obtained
as follows: 34.4 parts of 2-amino-benzene-sulphonic acid are
dissolved in 120 parts of water to form a neutral solution and
are diazotised in the usual way, The diazo compound is
then run, at 0 - 5, into a mixture of 56.2 parts of 2-
acetamino-5-naphthol-7-sulphonic acid, dissolved in 300 parts
of water to form the neutral solution, 25 parts of sodium
bicarbonate and 150 parts of ice, The pH value is at first
6.5 and rises to 7,5 - 7.8 after prolonged stirring. After
completion of the coupling, 60 parts of 10 normal sodium
hydroxide solution are added and the mixture is warmed to 90
for 2 hours in order to saponify the acetamino group, The,
alkaline solution of the orange intermediate dyestuf~ i9 neu-
tralised with about 22 parts of 10 normal hydrochloric acid,
20% strength sodium chloride and 15% strength potassium chlor-
ide are added and the mixture is stirred for some time and
flltered .
Equally valuable dyestuffs according to the invention
are obtained if the 2-amino-benzenesulphonic acid is replaced
by molar quantities of one of the diazo components mentioned
in the following text and if the procedure is in other respects

- 39 -

" ~o~7~ Ref, 3062



as described: 3-amino-benzene-sulphonic acid, 4-amino-benzene-
sulphonic acid, 2-naphthylamine-1,5-disulphonic acid, 5-chloro-
2-amino-benzene-sulphonic acid, 6-chloro-2-amino-benzene-
sulphonic acid, 5-nitro-2-amino-benzene-sulphonic acid, 4-
chloro-3-amino-benzene-sulphonic acid, 6-chloro-3-amino-
benzene-sulphonic acid, 3-chloro-4-amino-benzene-sulphonic
acid, 2-amino-toluene-4-sulphonic acid, 2-amino-toluene-5-
sulphonic acid, 3-amino-toluene-6-sulphonic acid, 4-amino-
toluene-2-sulphonic acid, 4-amino-toluene-3-sulphonic acid, -`.
5-chloro-2-amino-toluene-3-sulphonic acid, 3-chloro-2-amino-
toluene-5-sulphonic acid, 6-chloro-3-amino-toluene-4-sulphonic
acid, 2-chloro-4-amino-toluene-5-sulphonic acid, 2-chloro-4- --
amino-toluene-6-sulphonic acid, 4-nitro-2-amino-toluene-6-
sulphonic acid, 6-nitro-4-amino-toluene-2-sulphonic acid, 3-
amino-1,2-dimethyl-benzene-4-sulphonic acid, 4-amino-1,3-
dimethyl-benzene-5-sulphonic acid, 4-amino-1,3-dimethyl-benzene-
6-sulphonic acid, 2-amino-anisole-4-sulphonic acid, 4-amino-
anisole-2-sulphonic acid, 4-amino-anisole-3-sulphonic acid,
4-chloro-2-amino-anisole-5-sulphonic acid, 4-amino-phenetole-
2-sulphonic acid, 4-amino-phenetole-3-sulphonic acid, 2-amino-
phenetole-4-sulphonic acid, 4-amino-benæene-1,3-disulphonic
acid, 2-amino-benzene-1,4-disulphonic acid, 2-amino-toluene-
3,4-disulphonic acid, 2-amino-toluene-3,5-disulphonic acid,
aniline, 4-amino-toluene, 8-amino-anisole, 4-amino-chloro-
benzene, 2-amino-chlorobenzene, 2-naphthylamine-1-sulphonic
acid, 2-naphthylamine-5-sulphonic acid, 2-naphthylamine-6-
sulphonic acid, 2-naphthylamine-7-sulphonic acid, 2-naphthyl-
amine-8-sulphonic acid, 2-naphthylamine-1,7-disulphonic acid,

- 40 -

10~7172 Ref. ~062


2-naphthylamine-3,6-disulphonic acid, 2-naphthylamine-3,7-
disulphonic acid, 2-naphthylamine-4,7-disulphonic acid, 2-
naphthylamine-5,7-disulphonic acid, 2-naphthylamine-6,8-
disulphonic acid, 2-naphthylamine-1,5,7-trisulphonic acid,
2-naphthylamine-3,6,8-trisulphonic acid and 2-naphthylamine-
4,6,8-trisulphonic acid.
Equally valuable dyestuffs according to the invention
are obtained if the 2-acetamino-5-naphthol-7-sulphonic acid
which is employed as the coupling component for the preparation
of the starting dyestuff is replaced by molar quantities of the
acetyl compound of one of the coupling components mentioned in
the following text and if the procedure is in other respects
as described above: l-amino-8-naphthol-4,6-disulphonic acid,
2-amino-8-naphthol-6-sulphonic acid, 2-methylamino-8-naphthol-
6-sulphonic acid, 2-carboxymethylamino-8-naphthol-6-sulphonic
acid, 2-~-sulphoethylamino-8-naphthol-6-sulphonic acid, 2-
iso-propylamino-8-naphthol-6-sulphonic acid, 1-amino-8-naphthol-
3,5-disulphonic acid, 2-methylamino-5-naphthol-7-sulphonic acid,
2-ethylamino-5-naphthol-7-sulphonic acid, 2-n-butylamino-5-
naphthol-7-sulphonic acid, 1-amino-8-naphthol-4-sulphonic acid,
2-amino-8-naphthol-4-sulphonic acid and 2-amino-5-naphthol-
4,7-disulphonic acid.
Example 3:
Equally valuable dyestu~fs according to the invention
are obtained if the 36.3 parts of bis-[~ -chloroethyl-
sulphonyl)-ethyl]-amine hydrochloride in Example 1 are replaced
by 37.6 g o~ the corresponding sulphate or by a molar quantity
of the hydrochloride of one of the amines mentioned in the

- 41 -

; Ref. 3062
1~717Z

following text~ -cbloroethyl-sulphonyl)-ethyl-amine,~- -
(~-bromoethyl-sulphonyl)-ethyl-amine, ~-vinylsulphonyl-ethyl-
amine, y-(~-chloroethyl-sulphonyl)-propyl-amine, a-(~-chloro- - .
ethyl-sulphonyl)-isopropyl-amine~ -chloroethyl-sulphonyl)-
butyl-amine, ~ -chloroethyl-sulphonyl)-isobutyl-amine,-(~-
chloroethyl-sulphonyl)-pentyl-amine, ~ chloroethyl-sulpho-
nyl)-hexyl-amine, N-methyl-N-~ -chloroethyl-sùlphonyl)-
ethyl-amine, N-ethyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine,
N-propyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-butyl-N-
~ -chloroethyl-sulphonyl)-ethyl-amine, N-pentyl-N~
1 chloroethyl-sulphonyl)-ethyl-amine, N-hexyl-N-~ -chloroethyl-
sulphonyl)-ethyl-amine, N-nonyl-N-~ -chloroethyl-sulphonyl)-
ethyl-amine,N-dodecyl-N-~ -chloroethyl-sulphonyl)-ethyl-
amine, N-hexadecyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine,
N-octadecyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-
carboxymethyl-N-~ -bromoethyl-sulphonyl)-ethyl-amine~ N-
sulphatomethyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-
~-carboxyethyl-N-r-(~-chloroethyl-sulphonyl)-propyl-amine,
N-~-sulphatoethyl-N-y-(~-chloroethyl-sulphonyl)-propyl-am~ne,
N-~-sulphatoethyl-N-~ -chloroethyl-sulphonyl)-butyl-amine,
N-~-ethoxyethyl-N-~ -chloroethyl-sulphonyl)-butyl-amine,
N-r-chloropropyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine,
N-phenyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-p-chloro-
phenyl-N~ -chloroethyl-sulphonyl)ethyl-amine, N-o-methyl-
phenyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-p-methoxy-
phenyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-m-sulpho-
phenyl-N-~ -chloroethyl-sulphonyl)-ethyl-amine, N-p-sulpho-
phenyl-N-~ chloroethyl-sulphonyl)-ethyl-amine, bis-~




42

-
"- Ref. 3062
-; 10~7172

chloroethyl-sulphonyl)-ethyl]-amine, bis-[~ -bromoethyl-
sulphonyl)-ethyl]-amine, bis-[Y-(~-chloroethyl-sulphonyl)-
propyl]-amine, bis-[~ -chloroethyl-sulphonyl)-butyl]-amine
and bis-(~-vinyl-sulphonyl-ethyl)-amine.
ExamPle 4:
Equally valuable dyestuffs according to the invention
are obtained if the 18,5 parts of cyanuric chloride in Example
2 are replacedbythe molar quantity of one of the derivatives
of 1,3,5-triazine mentioned in the following text: tribromo-
triazine, trifluorotriazine, trisulphotriazine, tris-methyl-
sulphonyltriazine, tris-ethylsulphonyltriazine, tris-phenyl-
sulphonyltriazine, dichlorofluorotriazine, chloro-disulpho-
triazine and chloro-bis-methylsulphonyltriazine.
Example 5:
76.6 parts of 2-naphthylamine-4,6,8-trisulphonic acid
are dissolved in 250 parts of water to form a neutral solution.
50 parts of 4 normal sodium nitrite solution are added.
This mixture is run into a mixture of 50 parts of 10 normal
hydrochloric acid and 400 parts of ice. A solution of 21.4
parts of 3-toluidine in 100 parts of water and 20 parts of 10
normal hydrochloric acid is added, at 0 - 5, to the suspen-
sion of the diazo compound. The pH value is first reduced
to 3.5 with 150 parts of 4 normal sodium acetate solution and
is then raised to a value of 5.5 with sodium hydroxide solution.
After the coupling is complete, the mixture is filtered.
50.1 parts of the dyestuff 2-(4-amino-2-methyl-
phenylazo)-napthalene-4,6,8-trisulphonic acid prepared in this
way are dissolved in 250 parts of water to form a neutral

- 43 -

~ Ref.3062
37'17$~


solution. This neutral solution is added to a suspension,
prepared as in Example 1, of cyanuric chloride in acetone and
water. The temperatue is kept at -1 to 3 by cooling with --
ice. In the course of the acylation reaction 9 g of bicar-
bonate are introduced in such a way that the pH remains
between 5.5 and 7. When starting dyestuff can no longer be
detected in a chromatogram, 36.3 g of bis-[~ -chloroethyl-
sulphonyl)-ethyl]-amine hydrochloride are added in the form of
an approximately 50% strength paste and the mixture is warmed
to 50 . The pH value is kept within the limits of 4.5 -
6.0 by adding a further 18 g of bicarbonate. The reaction
is complete when further alkali is no longer consumed. The
resultlng dyestuff of the formula:

~03S ~ N - N ~ NH ~ N(cH2cH2so2cH2c~2cl)2

~3~ Cl

is precipitated by adding sodium chloride and dried in vacuo
at 50 - 75.
Similarly valuable reactive dyestuffs are also obtained
if the azo dye~tuffs which can be obtained from the diazo com-
ponents and coupling components indicated in the table which
follows are employed instead of the starting dyestuff employed
above, 2-(4-amino-2-methyl-phenylazo)-naphthalene-4,6,8-
trisulphonic acid, and if the procedure is in other respects
as described above.


- 44 -

Ref. 3062
1~g3717Z


Diazo components:
2-Naphthylamine-1,5-disulphonic acid, 2-naphthylamine-
4,8-disulphonic acid, 2-naphthylamine-5,7-disulphonic acid,
2-naphthylamine-6,8-disulphonic acid, 2-naphthylamine-1,5,7-
trisulphonic acid, 2-naphthylamine-3,6,8-trisulphonic acid and
aniline-2,5-disulphonic acid.
CouPlin~ comPonents:
Aniline, N-methylaniline, 3-amino-anisole, 3-amino-
toluene, 2-amino-4-acetamino-toluene, 2-amino-4-acetamino-
anisole, 3-amino-acetanilide, 3-amino-4-methoxy-toluene, 3-
amino-phenylurea, l-naphthylamine-6-sulphonic acid, 1-
naphthylamine-7-sulphonic acid and 1-naphthylamine-8-sulphonic
acid.
Example 6:
63.1 parts of 1-[2'-sulpho-4-(3,5-dichlorotriazinyl-
amino)-phenyl]-3-carboxy-4-(2-sulphophenylazo)-pyrazol-5-one
are dissolved in water at pH 6.8 - 7.2. 36.3 parts of bis-
[~ -chloroethyl-sulphonyl)-ethyl]-amine are added to this
solution at about 25 and the mixture is warmed to 35 - 40.
The pH begins to fall. When it has reached a value of
about 3.5, it is kept within the range from 3.5 to 4.5 by
adding approximately 11 g of sodium carbonate in portions.
The reaction is complete after about 3 hours, which can be
recognised from the fact that no fur~her alkali is con-
sumed. The pH of the dyestuff solution is now adjusted to
7.0 by adding disodium hydrogen phosphate. The resulting
dyestuff of the structure:


- 45 -

~' Ref. 3062
1087~72


SO3
N - N ~ COO~
3~




N(CH2CH2S02CH2C112Cl)2

1

can be isolated by salting-out or by spray-drying.
PreParation of the startin~ dyestuff:
49.7 parts of the yellow azo dyestuff obtained in
accordance with DAS 1,922,940, Example 2, from diazotised 1-
amino-benzene-2-sulphonic acid and 1-(4-amino-2-sulpho-phenyl)-
5-pyrazolone-3-carboxylic acid, are dissolved to form a neutral
solution and are reacted at 0 - 5 and at pH 6.5 with a sus-
pension of 18.5 parts of cyanuric chloride, prepared in water/
acetone by the method of Example 1. Approximately 6 parts
of sodium carbonate are added in order to maintain the pH
range. The reaction is complete when the dyestuff can no
longer be diazotised.
Similar valuable reactive dyestuffs according to the
invention are obtained if, instead of the intermediate dye-
stuff employed above, the condensation products, with cyanuric
chloride, of the azodyestuffs which can be obtained from the
diazo components and coupling components indicated in the
table which follows are employed and if the procedure is in
other respects as described above.

- 46 -

r~ Ref. 3062
72
~;
'
Diazo comPonents:
3-Amino-benzene-sulphonic acid, 4-amino-benzene-
sulphonic acid, 5-chloro-2-amino-benzene-sulphonic acid, 2,5-
dichloro-4-amino-benzene-sulphonic acid, 2-amino-toluene-4-
sulphonic acid, 4-amino-toluene-3-sulphonic acid, 2-amino-
anisole-4-sulphonic acid, 4-amino-benzene-1,3-disulphonic acid,
2-amino-benzene-1,4-disulphonic acid, 2-amino-toluene-3,5-
disulphonic acid, 2-amino-naphthalene-1,5-disulphonic acid,
2-amino-naphthalene-4,8-disulphonic acid, 2-amino-6,8-
disulphonic acid, 2-amino-naphthalene-1-sulphonic acid and
2-amino-naphthalene-6-sulphonic acid.
CouPlin~ comPonents:
1-(3-Amino-6-sulpho-phenyl)-3-methyl-5-pyrazolone, 1-
(4-amino-3-sulpho-phenyl)-3-methyl-5-pyrazolone, 1-(4-amino-
2-sulpho-phenyl)-3-methyl-5-pyrazolone, 1-(3-amino-6-sulpho-
phenyl)-5-pyrazolone-3-carboxylic acid, 1-(4-amino-3-sulpho-
phenyl)-5-pyrazolone-3-carboxylic acid, 1-(3-amino-5-sulpho-
; 6-methyl-phenyl)-5-pyrazolone-3-carboxylic acid, 1-(2-methyl-
3-amino-5-sulpho-phenyl)-5-pyrazolone-3-carboxylic acid, 1-
(2-methyl-3-amino-5-sulpho-phenyl)-3-methyl-5-pyrazolone, 1-
(3-amino-5-sulpho-6-methyl-phenyl)-3-methyl-5-pyrazolone and
1-(4-amino-2,5-disulpho-phenyl)-5-pyrazolone-3-carboxylic acid,
ExamPle 7:
50.3 parts of the monoazo dyestuff 1-(5'-amino-2'-
sulpho-phenylazo)-2-naphthol-6,8-disulphonic acid are first
reacted, at 0 - 5 and at a pH value of 6 - 6.5, with a sus-
pension of 18.5 parts of cyanuric chloride which has been
prepared by dissolving the cyanuric chloride in 100 parts of
.
- 47 -




. .

` ~ Ref. 3062
37~7Z

acetone and precipitating with 250 g of ice, and the product
is then reacted, at 30 - 40 and at a pH value of 4.0 - 4.5,
with 36.3 parts of bis-[~ -chloroethyl-sulphonyl)-ethyl]-
amine hydrochloride. me resulting orange reactive dye-
stuff of the formula

~1 . 0

(Cl-C~2-C~2-s02-c~2 C~2)2 N ~ NH ~ 0

~03S
so3~

is obtained by concentrating the neutral solution to dryness
in vacuo at 55 - 60, or is precipitated with sodium chloride,
and is filtered off and dried in vacuo.
The starting dyestuff, 1-(5-amino-2-sulpho-phenylazo)-
2-naphthol-6,8-disulphonic acid,is obtained by coupling diazo-
tised 2-amino-4-acetamino-benzene-sulphonic acid with 2-
naphthol-6,8-disulphonic acid and subsequently saponifying the
:
acetyl group with ~odium hydroxide solution or hydrochloric
acid,
Similar valuable reactive dyestuffs according to the
invention are obtained if monoazodyestuffs which contain amino
groups and which can be prepared from the diazo components and
coupling components in the following text, with subsequent
saponification of the acetyl group or reduction of the nitro
group, are used as the starting materials and if the procedure
is in other respects in accordance with the above instructions.

- 48 ~

Ref. 3062
~o~,7~q~

Diazo comPonents:
2-Amino-5-acetamino-benzene-sulphonic acid, 2-amino-4-
acetamino-toluene-5-sulphonic acid, 2-amino-4-acetamino-
toluene-6-sulphonic acid, 2-amino-6-acetamino-toluene-4-
sulphonic acid, 5-nitro-2-amino-benzene-sulphonic acid, 6-
acetamino-2-aminonaphthalene-4,8-disulphonic acid, 4-nitro-2-
amino-toluene-6-sulphonic acid, 6-nitro-4-amino-toluene-2-
sulphonic acid, 6-nitro-2-amino-naphthalene-8-sulphonic acid
and 6-nitro-2-amino-naphthalene-4,8-disulphonic acid.
CouPlin~ comPonents:
l-Naphthol-3,6-disulphonic acid, 1-naphthol-3,8-
disulphonic acid, l-naphthol-3,7-disulphonic acid, 2-naphthol-
3,7-disulphonic acid, 2-naphthol-4,8-disulphonic acid, 1-
naphthol-3,6,8-trisulphonic acid, 2-naphthol-3,6,8-trisulphonic
acid, 2-amino-naphthalene-3,6-disulphonic acid, 2-amino-
naphthalene-5,7-disulphonic acid, 1-(2- or 3- or 4-sulphophenyl)-
3-methyl-5-pyrazolone, 1-(2-methyl-4-sulphophenyl)-3-methyl-5-
pyrazolone, 1-(2,5-dichloro-4-sulphophenyl~-3-methyl-5-pyrazo-
lone, 1-(2,5-disulphophenyl)-3-methyl-5-pyrazolone, 1-(2- or 3-
or 4-su~phophenyl)-5- pyrazolone-3-carboxylic acid and 1-(2-
chloro-5-sulphophenyl)-5-pyrazolone-3-carboxylic acid.
ExamPle 8:
, .
65.1 parts of 1-dichlorotriazinylamino-8-naphthol-7-
(2-sulphophenylazo)-naphthalene-3,6-disulphonic acid are
stirred in 500 parts by volume of water at 40. 36.3 parts
of bis-[~ -chloroethylsulphonyl)-ethyl]-amine hydrochloride
are added to the suspension and stirring is continued at 40.
The pH value is kept between 3.8 and 4.2 by adding about 17

- 49 -

Ref. 3062
; 1~87~7Z `


parts of sodium bicarbonate. The reaction is complete when
the pH value has remained constant for about 3 hours. The
resulting dyestuff of the formula

, . ,
S3~ _ ~ N ~ (CH2-cH2-s2-cH2 CH2 Cl)2
N N ~ ~1
~03S so3
., .
is completely in solution. The pH of the solution is
adjusted to 7 and the dyestuff is isolated by salting-out
or by spray-drying.
Preparation of the startin~ dYestuff:
31.9 parts of 1-amino-8-naphthol-3,6-disulphonic acid
are dissolved in 150 parts by volume of water at 50 and at
pH 6. This solution is added in the course of about 90
minutes to a suspension of 20 parts of cyanuric chloride in
80 parts by volume of water and 60 parts by volume of acetone
at a temperature of 0 - 10 and the mixture is stirred until
free l-amino-8-naphthol-3,6-disulphonic acid can no longer be
detected. In the course of the reaction the pH value falls
to about 1,5. The diazo component which has been obtained
in the customary manner by diazotising 17.3 parts of aniline-
o-sulphonic acid is added to the suspension of the coupling
component obtained in this way and the coupling is completed
at a pH value of about 6.5. The dyestuff i9 precipitated
by adding 10% strength by volume sodium chloride and is fil-
tered off and washed with 300 parts by volume of 10% strength

- 50 -

1~871~2 Ref. 3062
.

sodium chloride solution.
ExamPle 9:
50.3 parts of the dyestuff 1-amino-4-(3-amino-4-
methyl-5'-sulpho-phenyl-amino)-anthraquinone-2-sulphonic acid
are dissolved in water and the necessary quantity of sodium
carbonate to form a neutral solution. This solution is
added at 0 - 5 to a suspension of 18.5 parts of cyanuric
chloride which has been prepared by dropwise addition of the
cyanuric chloride dissolved in 110 parts of acetone to 250
parts of ice. The hydrogen chloride formed in the reaction
is neutralised by adding 50 parts of 2 normal sodium carbonate
solution dropwise, a pH value of 6 - 6.5 being produced.
36.3 parts of bis-[~ -chloroethyl-sulphonyl)-ethyl]-amine
hydrochloride are then added and the mixture is warmed to 30
- 40 and this temperature -is maintained for 3 hours. At
the same time, the pH value is kept at 4.0 - 4.5 by adding
100 parts of 2 normal sodium carbonate solution dropwise.
The resulting reactive dyestuff of the formula
,~
. Q N ~ Cl

-- ~1 N(CH2-C~I2-S02-CI~2 CE~2 Cl)2
O N~ ~ C~3
\~/ . '
803~

is salted-out with sodium chloride, filtered off and dried at
55 - 60.
Similar valuable dyestuffs according to the invention

- 51 -



., . ' ' ' ' '.

Ref. 3062
lOB71`72


are obtained if the dyestuffs of the table which follows are
employed instead of the starting dyestuff l-amino-4-(3-amino-
4-methyl-5-sulpho-phenyl-amino)-anthraquinone-2-sulphonic
acid and if the procedure is in other respects as described
above.
Intermediate d~estuffs
l-Amino-4-(3-amino-4-sulpho-phenyl-amino)-anthraquinone-
2-sulphonic acid, 1-amino-4-(4-amino-3-sulpho-phenyl-amino)-
anthraguinone-2-sulphonic acid, 1-amino-4-(3-amino-2-methyl-5-
sulpho-phenyl-amino)-anthraquinone-2-sulphonic acid, l-amino-
4-(4-amino-2,2'-disulpho-diphenyl-(4')-amino)-anthraquinone-
2-sulphonic acid, 1-amino-4-(3-amino-4-methyl-5-sulpho-phenyl-
sulphonyl-phenyl-(3')-amino)-anthraquinone-2-sulphonic acid,
l-amino-4-(4-amino-phenyl-amino)-anthraquinone-2,5-disulphonic
acid and l-amino-4-(4'-amino-2,2'-disulpho-stilbyl-(4)-amino)-
anthraquinone-2-sulphonic acid.
Example 10:
106.6 parts of the dyestuff 3-(3-amino-4-sulpho-
phenyl-amino-sulphonyl)-copper-phthalocyanine-3',3",3"'-
trisulphonic acid are dissolved in water and the necessary
quantity of sodium carbonate to form a neutral solution.
This solution is run, at 0 - 5, into a suspension of 18.5
parts of cyanuric chloride which has been prepared by drop-
wise addition of the cyanuric chloride dissolved in 110 parts
of acetone to 250 parts of ice. The pH value is kept at
6 - 6.5 during the reaction by adding 50 ml of 2 normal sodium
carbonate solution dropwise. 36.3 parts of bis-[~
chloroethylsulphonyl)-ethyl]-amine hydrochloride are added to

- 52 -

Ref. 3062
~ 7~7Z


the resulting intermediate stage and the mixture is warmed at
~5 - 45 for 4 hours. At the same time, the pH value is
kept at 4.0 - 4.5 by adding 100 parts of 2 normal sodium hydrox-
ide solution dropwise The resùlting reactive dyestuff has
the following structure:
Cl




/ (S03~)3 ~
CuPc N~ ~--N(CH2CH2S02C~2c~2cl)2
SO~N~ ~ 3~

It is precipitated with sodium chloride, filtered off and
dried in vacuo at 55 - 60.
The dyestuff 3-(3'-amino-4'-sulpho-phenyl-amino-
sulphonyl)-copper-phthalocyanine-3',3",3"'-trisulphonic acid
which serves as the starting material can be prepared by
reacting copper phthalocyanine tetrasulphochloride with 2,4-
diamino-benzene-sulphonic acid in the presence of pyridine at
pH 5 - 9.
Similarly valuable dyestuffs according to the invention
are obtained if starting dyestuffs are employed which have
been prepared with 2,4-diamino-toluene-6-sulphonic acid, 2,5-
diamino-benzene-sulphonic acid, 2,6-diamino-toluene-4-sulphonic
acid, 4,4'-diamino-diphenyl-2,2'-disulphonic acid and 3,3'-
diamino-4-methyl-diphenyl-sulphone-5-sulphonic acid instead
of 2,4-diamino-benzene-sulphonic acid and i~ the reaction with
cyanuric chloride and bis-~ chloroethyl-sulphonyl)-ethyl]-
amine hydrochloride is carried out in other respects as des-
cribed above.

- 53 -



' '

` Ref. 3062
1~7~72
.

Similarly valuable reactive dyestuffs according to the
invention are also obtained if corresponding nickel phthalo-
cyani~e dyestuffs are used as starting materials instead o~
copper phthalocyanine dyestuffs.
Example 11
.




A neutral solution of 48.9 parts of 4-amino-4'-(2,6-
dinitro-4'-carboxy-phenyl-amino)-diphenylamine-2-sulphonic
acid is reacted at 0 - 5 with a suspension of 18.5 parts of
cyanuric chloride which has been obtained by dropwise addition
of the cyanuric chloride dissolved in 110 parts of acetone to
250 parts of ice. The pH value is kept at 6.0 - 6.5 by
adding 50 parts of 2 normal sodium hydroxide solution in por-
tions. After the reaction is complete, ~6.3 parts of bis-
[~ -chloroethyl-sulphonyl)-ethyl]-amine hydrochloride are
added in the form of a powder and the mixture is warmed to 30
- 40 and this temperature is maintained for 3 hours, the pH
value being kept at 4.0 - 4.5 with 100 parts of 2 normal sodium
hydroxide solution. The resulting yellow-brown reactive
dyestuff has the following structure:

NO2 ~3~
HOOC~NB~_NB~3_NEI~N(CH2CH2S02CH2CB2C1)2

2

It is precipitated with sodium chloride, filtered off and dried
at 55 - 60.
The starting dyestuff which is used, 4-amino-4'-(2,6-

- 54 -

Ref. ~062
10~371~2


dinitro-4-carboxy-phenyl-amino)-diphenylamine-2-sulphonic acid
can be prepared in the following way: 27,9 parts of 4,4'-
diamino-diphenylamine-2-sulphonic acid are dissolved in water
to form a neutral solution. 24.7 parts of 1-chloro-2,6-
dinitro-benzene-4-carboxylic acid and 8.~ parts of anhydrous
sodium acetate are added to the mixture, which is boiled for
5 - 6 hours at 95 - 98 and the condensation product is pre-
cipitated as the sodium salt.
Example 12:
58.1 parts of the copper complex dyestuff prepared by
diazotising 2-aminophenol-4,6-disulphonic acid and coupling
the product with 2-amino-5-naphthol-7-sulphonic acid, followed
by coppering in acetic acid solution, are dissolved in water
to form a neutral solution. This dyestuff solution is run,
at 0 - 5, into a suspension of 18.5 parts of cyanuric chlor-
ide which has been prepared by dissolving the cyanuric chlorlde
in 110 parts of acetone and adding the solution dropwise to
250 parts of ice. The pH value is kept at 4.5 - 5.5 during
the reaction by adding 50 parts of 2 normal sodium carbonate
solution dropwise. Stirring is continued for a further 1 -
2 hours at 0 - 5 until the reaction is complete, 36,5
parts of bis-~ -chloroethyl-sulphonyl)-ethyl]-amine hydro-
chloride are then added and the mixture is warmed to approxi-
mately 45 and the pH value is kept at 4.5 - 5.0 by adding 100
parts of 2 normal sodium carbonate solution in portions.
The resulting ruby-red reactive dyestuff corresponds to the
following formula:


- 55 -

-~ Ref. 3062
7~72
.; ' ,

o--cu o~
N(CH2C~2S02cE2c~2cl )2
~03S ~ - N - N ~ ~H

S03H 3

It is precipitated with sodium chloride, f~iltered o~f and
dried at 55 - 60.
Similarly valuable reactive dyestuffs according to the
invention are obtained if the copper complex dyestuffs o~
the dyestuffs prepared from the diazo components and coupling
components in the following text are employed as the starting
dyestuffs instead of the copper complex dyestuf~ from 2-amino-
phenol-4,6-disulphonic acid and 2-amino-5-naphthol-7-sulphonic
acid, and if the reactions with cyanuric chloride and bis-[~-
-chloro-ethyl-sulphonyl)-ethyl]-amine hydrochloride are
carried out in other respects as described above.
Diazo ~E~nents:
2-~mino-phenol-4-sulphonic acid, 2-amino-phenol-5-
sulphonic acid, 6-nitro-2-amino-phenol-4-sulphonic acid, 4-
nitro-2-amino-phenol-6-sulphonic acid, 4-chloro-2-amino-phenol-
6-sulphonic acid, 2-amino-4-methyl-phenol-6-sulphonic acid,
2-amino-4-acetamino-phenol-6-sulphonic acid, 1-amino-2-naphthol-
4-sulphonic acid and 6-nitro-1-amino-2-naphthol-4-sulphonic
acid.
Couplin~ components:
l-Amino-5-naphthol-7-sulphonic acid, 1-amino-8-
naphthol-4-sulphonic acid, 1-amino-8-naphthol-6-sulphonic acid,
2-(N-methylamino)-5-naphthol-7-sulphonic acid~ 2-(N-ethylamino)-


- 56 -

" Ref. 3062
10~7172

5-naphthol-7-sulphonic acid, 2-(N-hydroxyethylamino-5-naphthol-
7-sulphonic acid, 2-amino-8-naphthol-6-sulphonic acid, 2-(N-
methylamino)-8-naphthol-6-sulphonic acid, 2-(N-ethylamino)-8-
naphthol-6-sulphonic acid, 1-amino-8-naphthol-3,6-disulphonic
acid, l-amino-8-naphthol-4,6-disulphonic acid, 2-amino-5-
naphthol-1,7-disulphonic acid and 2-amin~-8-naphthol-3,6-
disulphonic acid.
ple 13:
36.3 parts of bis-[~ -chloroethyl-sulphonyl)-ethyl]-
amine hydrochloride are added, in the form of powder, to a sus-
pension of 79.4 parts of the copper complex of 7-[6-(3,5-
dichloro-2,4,6-triazinyl-amino)-2-hydroxy-4-sulpho-1-naphthyl-
azo]-l-amino-8-hydroxy-naphthalene-2,4-disulphonic acid in
approximately 800 parts of water at 0 - 5 and having a pH
value of 6.5. The mixture is warmed to ~0 - 40 and this
temperature is maintained for 4 hours. At the same time,
the pH value is kept at 4.0 - 4.5 by adding 100 parts of 2
normal sodium carbonate solution dropwise. The end of
the reaction is recognised by the fact that the pH value
remains constant at 4.5. The blue reactive dyestuff which
is prepared has the following structure:


HO~S SD3H


NH

Cl ~ ~(C~2CH2502CH2cH2cL)2

- 57 -

--~ Ref. 3062
101~172
.
It is either concentrated by evaporation in vacuo at 55 - 60
or precipitated with sodium chloride.
The copper complex of 7-~6-(3,5-dichloro-2,4,6-
triazinyl-amino)-2-hydroxy-4-sulpho-1-naphthylazo]-1-amino-
8-hydroxy-naphthalene-2,4-disulphonic acid which is used as
the starting dyestuff is prepared in the following way: 60.8
parts of 6-nitro-1-diazonio-4-sulpho-2-naphtholate are coupled
with 63.8 parts of 1-amino-8-hydroxy-naphthalene-2,4-disulphonic
acid at 0 - 5 in the presence of sodium carbonate. In order to
reduce the nitro group, a solution o~ 27.3 parts of sodium sul-
phide in water i~ added dropwise to the dyestuff solution at
about 40 - 50 and stirring i~ continued for 1 - 2 hours.
The dyestuff, which containsamino groups, is precipitated with
sodium chloride, filtered off and dissolved in about 800 parts
of water and the pH of the solution is adjusted to 5 - 5.3
with acetic acid. 40 parts of copper acetate or 50 parts
of copper sulphate are added to the mixture, which is stirred
for 5 hours at 20 - 30. The resulting copper complex
dyestuff is precipitated with sodium chloride, filtered off
and dissolved in 800 parts of water to form a neutral solution.
The dyestuff solution is then run, at 0 - 5, into a suspen-
sion of 37.0 parts of cyanuric chloride which has been
prepared by dropwise addition of the cyanuric chloride dis-
solved in 200 parts of acetone to 500 parts of ice. Stir-
ring is continued for 1 - 2 hours at 0 - 5, until diazotisable
amino groups can no longer be detected.
Similarly valuable reactive dyestuffs according to the
invention are obtained if the diazo compounds of the amines

- 58 -

Ref. 3062
1~7172


which follow are employed instead of 6-nitro-1-diazonio-4-
sulpho-naphtholate: 4-nitro-2-amino-1-hydroxy-naphthalene-
6-sulphonic acid, 6-nitro-2-amino-phenol-4-sulphonic acid and
4-nitro-2-amino-phenol-6-sulphonic acid.
ExamPle 14:
36.3 parts of bis-[~ -chloroethyl-sulphonyl)-ethyl]-
amine hydrochloride are added, in the form of powder, to a
neutral dyestuff suspension of 82.4 parts of the copper com-
plex of N-(2-hydroxy-4-sulpho-phenyl)-N'-(2-carboxy-4-sulpho-
phenyl)-ms-[4-(~,5-dichloro-2,4,6-triazinyl-amino)-2-sulpho-
phenyl]-formazan in approximately 800 parts of water, the
temperature being about 0 - 5. The mixture is then warmed
for 4 hours at 30 - 40 and the pH value is kept at 4.0 - 4.5
during this time by adding dilute sodium hydroxide solution in
portions. When sodium hydroxide solution is no longer
required, that is to say when the pH value remains constant,
the blue reactive dyestuff which has been prepared is iso-
lated by spray-drying at 55 - 60 or by salting-out. It
has the following structure:

~ 03S~FOO`C ~ ----~ SS
I d
~C'' . . .
S03

NH

L Cl ~ N(cH2c~2so2c~2cH2cl)2 ¦ 4H

- 59 -

~ Ref. 3062
1087172

The copper complex of N-(2-hydroxy-4-sulpho-phenyl)-N'-(2-
carboxy-4-sulpho-phenyl)-ms-[4-(3,5-dichloro-2,4,6-triazinyl-
amino)-2-sulpho-phenyl]-formazan which serves as the starting
dyestuff is obtained in the following way: 46.4 parts of 2-
carboxy-phenylhydrazine-4-sulphonic acid and 48.6 parts of 4-
acetamino-benzaldehyde-2-sulphonic acid are subjected to a
condensation reaction in aqueous solution and the resulting
hydrazone is coupled, in the presence of sodium carbonate and
at 0 - 5, with the diazo compound of 37.8 parts of l-amino-
2-hydroxy-benzene-4-sulphonic acid. The formazan which is
formed is adjusted with acetic acid to pH 5 - 5.3 and is con-
verted into the copper complex with copper donors, such as,
for example, 40 parts of copper acetate or 50 parts of copper
sulphate, by warming at 40 - 50 for 5 hours. This copper
complex is precipitated with sodium chloride and is dissolved
in approximately 800 ml of water to forma neutral solution.
The dyestuff solution is run, at 0 - 5, into a suspension of
~7.0 parts of cyanuric chloride which is prepared by dis-
solving the cyanuric chloride in 200 parts of acetone and
precipitating with 500 parts of ice. The mixture is stirred
for 1 - 2 hours at 0 - 5 until complete reaction has taken
place.
Similarly valuable reactive dyestuffs according to the
invention are obtained if formazans are prepared from the hydra-
zine, aldehyde and diazo components which follow, wherein at
least one acetamino group must be present, in the aldehyde
component or in the diazo component according to choice, the
formazans are converted into the copper complex, the acetamino

- 60 -

--10~71~2 Ref. 3062
.


group is saponified, the dyestuffs are reacted with cyanuric -
chloride and the procedure is in other respects as indicated
above. The components should also be chosen in such a way
that at least three sulphonic acid groups are present per dye-
stuff molecule. If a saponifiable acetamino group is
present in each of the aldehyde and diazo components, reactive
radicals can be introduced into the dyestuff in two places.
HYdrazine comPOnents:
2-Hydroxy-phenylhydrazine, 6-nitro-2-hydroxy-phenyl-
hydrazine, 4-chloro-2-carboxy-phenylhydrazine, 5-nitro-2-
carboxy-phenylhydrazine, 4-methoxy-2-carboxy-phenylhydrazine,
4-nitro-2-hydroxy-6-sulpho-phenylhydrazine, 6-nitro-2-hydroxy-
4-sulpho-phenylhydrazine, 2-carboxy-5-sulpho-phenylhydrazine,
2-hydroxy-6-carboxy-4-sulpho-phenylhydra7ine, 2-hydroxy-4,6-
disulpho-phenylhydrazine, 2-hydroxy-4-sulpho-naphthylhydrazine
and 2-hydroxy-4,6'-disulpho-naphthyl-1-hydrazine.
; deh~de comPonents: ~ -
Benzaldehyde, 4-methyl-benzaldehyde, benzaldehyde-2-
or 3- or 4-sulphonic acid, benzaldehyde-2,4-disulphonic acid,
2- or 3- or 4-nitro-benzaldehyde, 2-chloro-benzaldehyde-5-
- ~ ~ sulphonic acid, 2- or 3- or 4-acetamino-benzaldehyde, 3-
acetamino-benzaldehyde-4-sulphonic acid and 5-acetamino-
benzaldehyde-2-sulphonic acid.
Diazo components:
l-Amino-3-acetamino-2-hydroxy-benzene-5-sulphonic acid,
l-amino-5-acetamino-2-hydroxy-benzene-3-sulphonic acid, 3-
chloro-l-amino-2-hydroxy-benzene-5-sulphonic acid, 5-nitro-1-
amino-2-hydroxy-benzene-3-sulphonic acid, 5-nitro-1-amino-2-


- 61 -




:. , , : - . , ~ . ,

'


10~7172 . Ref. 3062


hydroxy-benzene-4-sulphonic acid and 1-amino-2-hydroxy-
benzene-4,6-disulphonic acid.
Example 15:
A suspension of 36.5 parts of bis-[~ -chloroethyl-
sulphonyl)-ethyl]-amine hydrochloride is added, at O - 5~ to
a suspension in 800 parts of water of 91.9 parts of the
dichloro-triazinyl-amino-phenylene which can be obtained in
accordance with German Offenlegungsschrift 2,305,990, Example
31, and the mixture is heated for 3 - 4 hours at 30 - 40.
The hydrogen chloride which is eliminated is neutralised by
adding 100 parts of 2 normal sodium hydroxide solution drop-
wise and the pH value is kept at 4.0 - 4.5. The reaction
is complete when the pH value remains constant. The blue
reactive dyestuff which is obtained is concentrated by evapora-
tion in vacuo at 55 - 60 or is precipitated with sodium
chloride~ It corresponds to the following formula:
S03H

~03S ~ ~ _ W ~ N ~ N(CN2c~2s2c~ac~2cl~2
~ o3~ ll


C~3 C~3
ExamPle 16:
An aqueous suspension of 72.6 parts of bis-C~
chloroethyl-sulphonyl)-ethyl~-amine hydrochloride is run, at
O - 5, into an aqueous suspension of 81.4 parts of the N,N-


- 62 -

~' Ref. 3062
~0~717Z

bis-(3,5-dichloro-2,4,6-triazinyl) compound of 7-(5-amino-2-
sulpho-phenylazo)-l-amino-8-naphthol-3,6-disulphonic acid.
The mixture is then warmed to 30 - 40, this temperature is
maintained for 3 - 4 hours and, simultaneously, a solution of
100 parts of 2 normal sodium carbonate solution is run in
dropwise, in portions, in order to keep the pH value at 4.0 -
4.5. The reaction is complete when the pH value remains
constant. The bluish-tinged red reactive dyestuff which
is obtained is either concentrated by evaporation at 55 - 60
in vacuo or is precipitated with sodium chloride. It has
the following structure:



~H03S so3~ ~(CH2CH2S02cH2cH2cl)2

~ .
Cl ~ N(CH2C~2s02c~2c~2cl~2

The N,N'-bis-(3,5-dichloro-2,4,6-triazinyl) compound o~ 7-
(5-amino-2-sulpho-phenylazo)-1-amino-8-naphthol-3,6-disulphonic
acid which serves as the starting dyestuff i9 obtained by
the following route: a neutral solution of 37.6 parts of 2,4-
diamino-benzene-sulphonic acid is reacted at a temperature of
0 - 5 and a pH value of 6 - 7 with a suspension of 37.0
parts of cyanuric chloride, and a neutral solution of 63.8
parts of l-amino-8-naphthol-3,6-disulphonic acid is reacted
at a temperature of 0 - 5 and a pH value of 6 - 7 with a

- 63 -

Ref. 3062
717Z

suspension of 37.0 parts of cyanuric chloride. In both
cases the pH value of 6 - 7 is maintained by adding, in each
case, 100 parts of 2 normal sodium carbonate solution drop-
wise. The diazo component, 2-amino-5-(3,5-dichloro-2,4,6-
triazinyl-amino)-benzene-sulphonic acid is diazotised in
hydrochloric acid solution in the customary manner at 0 - 5
with sodium nitrite and is then combined with the coupling
component, l-(3,5-dichloro-2,4,6-triazinyl-amino)-8-naphthol-
3,6-disulphonic acid, to give the monoazo dyestuff.
Similarly valuable reactive dyestuffs according to the
invention are obtained if, in the preparation of the starting
dyestuff, the condensation products, with cyanuric chloride,
of the coupling components mentioned in Example 1 are employed
instead of the condensation product of l-amino-8-naphthol-3,6-
disulphonic acid with cyanuric chloride and if the procedure
is in other respects as described above.
Equally valuable dyestuffs according to the invention
are obtained if the condensation product of 2,4-diaminobenzene-
sulphonic acid with cyanuric chloride which is employed as the
diazo component in the manufacture of the starting dyestuff,
is replaced by the corresponding condensation products of
cyanuric chloride with 2,5-diaminobenzenesulphonic acid or
2,5-diaminobenzene-1,4-disulphonic acid and if the procedure
is in other respects as described above.
Example 17:
A neutral solution of 72.8 parts of the copper com-
plex of the dyestuff 6-amino-1,2',8'-trihydroxy-2,1'-azo-
naphthalene-3',4,6',8-tetrasulphonic acid in 400 parts of water

- 64 -

~' Ref. 3062
~3717Z


is run, at O - 5, into a suspension of 18 .5 parts of cyanuric
chloride which has been dissolved in 70 parts of warm acetone
and added to 300 parts of ice while stirring. The hydro-
chloric acid which is formed in the reaction is neutralised
(pH value 5,5 - 6.5) by adding 50 parts of 2 normal sodium
hydroxide solution dropwise. 36.3 parts of bis-[~
chloroethyl-sulphonyl)-ethyl]-amine hydrochloride are then
added in the form of a powder. me mixture is warmed to
40 in the course of approximately ~ hour and this temperature
is maintained for 3 hours. At the same time, the pH value
is kept at 4.0 - 4.5 by adding 17 g of sodium bicarbonate.
The blue reactive dyestuff of the formula

Ho3S - Cu - S03H Cl

N - N ~ ~ ~
OH ~ N~ N(cH2cH2so2cH2cH2 2
~O3S
~O38
,.
which is obtained is salted-out with sodium chloride, filtered
off and dried in vacuo at 60.
The copper complex dyestuff which is used as the star-
ting material is prepared in the following way in accordance
with the instructions of German Paten~ Specification 1,117,235:
81.8 parts of the 0-benzenesulphonyl ester of 1-amino-8-
naphthol-3,6-disulphonic acid are diazotised and are coupled
with 72.2 parts of 2-acetamino-5-naphthol-4,8-disulphonic acid
in a medium alkaline with sodium carbonate. The resulting

- 65 -

-~ Ref, 3062
~ 717Z
.

.
monoazo dyestuff is converted into the copper complex in a
known manner by oxidative coppering using copper sulphate and
hydrogen peroxide in acetic acid solution and the benzene-
sulphonyl group and the acetyl group are then split off by
hydrolysis.
Equally valuable dyestuffs according to the invention
are obtained if, in the preparation of the starting dyestuff,
the diaæo component is replaced by molar quantities of the
diazo components which follow and if the procedure is in other
respects in accordance with the route described above: 1-
amino-8-naphthol-4,6-disulphonic acid 0-benzenesulphonyl ester,
l-amino-8-naphthol-4,7-disulphonic acid 0-benzenesulphonyl
ester, 2-amino-naphthalene-4,8-disulphonic acid, 2-amino-6-
nitro-naphthalene-4,8-disulphonic acid, 2-amino-naphthalene-
4,6,8-trisulphonic acid, 2-amino-naphthalene-6-sulphonic acid
and 2-amino-naphthalene-8-sulphonic acid.
Valuable dyestuffs according to the invention are fur-
ther obtained if, in the preparation of the starting dyestuff,
the coupling component 2-acetamino-5-naphthol-4,8-disulphonic
acid is replaced by molar quantities of the N-acetyl compound
of the following coupling components: 2-amino-8-naphthol-6-
sulphonic acid, 2-amino-5-naphthol-7-sulphonic acid, 2-amino-
5-naphthol-1,7-disulphonic acid and 2-amino-8-naphthol-3,6-
disulphonic acid.
Example 18:
70.2 parts of the disazo dyestuff 1-amino-2-(4-
sulphophenylazo)-7~(2-sulpho-5-aminophenylazo)-8-naphthol-
3,6-disulphonic acid are reacted, in the form of a neutral

- 66 -

Ref. 3062
10~717Z


solution at O - 5, with a suspension of 18.5 parts of cya-
nuric chloride which has been dissolved in 110 parts of acetone
and re-precipitated using 250 parts of ice. The reaction
is carried out at pH 6.0 - 6.5, the pH value being maintained
by adding 50 parts of 2 normal sodium carbonate solution drop-
wise. 36.3 parts of bis-[~ -chloroethyl-sulphonyl)-
ethyl]-amine hydrochloride are then added in the form of a
powder, the mixture is warmed to 30 - 40 and the pH value is
kept at 4.0 - 4.5 by adding 100 parts of 2 normal sodium car-
bonate solution dropwise. The resulting dyestuff of the
structure -

N~2 OH 3 Cl
~03S ~ N -N ~ ~ N ~N ~ ~ ~ ;
~03S ~ SO H ~ (c~2c~aso2c~2cH2clj2


is isolated by salting-out or by spray-drying.
The disazo dyestuff which serves as the starting
material can be prepared in the following way: the diazo com-
pound of 34.6 parts of sulphanilic acid is coupled, in a first
stage in an acid medium at pH 2 - 4~with 63.8 parts of 1-
amino-8-naphthol-3,6-disulphonic acid, and then in a second
~tage, in a medium alkaline with sodium carbonate, with the
diazo compound of 46.0 parts of 2-amino-4-acetamino-benzene-
sulphonic acid. The acetyl group of the disazo dyestuff
is saponified by warming at 90 - 100 in the presence of
excess sodium hydroxide solution.
Similarly valuable dyestuffs according to the invention

- 67 -




.: .

~0~717Z Ref. 3062


are obtained if the dyestuffs which follow are employed instead
of the disazo dyestuff employed as the starting dyestuff and
if the procedure is in other respects as described above:
l-amino-2-(2-sulphophenylazo)-7-(2-sulpho-5-aminophenylazo)-
8-naphthol-3,6-disulphonic acid, 1-amino-2-(2,4-disulphophenyl-
azo)-7-(2-sulpho-5-aminophenylazo)-8-naphthol-3,6-disulphonic
acid, l-amino-2-(2,5-disulphophenylazo)-7-(2-sulpho-5-amino-
phenylazo)-8-naphthol-3,6-disulphonic acid, 1-amino-2-(4-
sulphophenylazo)-7-(2-sulpho-4'-aminophenylazo)-8-naphthol-
3,6-disulphonic acid, 1-amino-2-(2,5-disulphophenylazo)-7-
(2-sulpho-4-aminophenylazo)-8-naphthol-3,6-disulphonic acid,
l-amino-2-(2-sulpho-4-aminophenylazo)-7-(4-sulphophenylazo)-
8-naphthol-3,6-disulphonic acid, 1-amino-2-(2-sulpho-4-amino-
phenylazo)-7-(2,5-disulphophenylazo)-8-naphthol-3,6-disulphonic
acid, l-amino-2-(2,5-disulpho-4-aminophenylazo)-7-phenylazo-8-
naphthol-3,6-disulphonic acid, 1-amino-2-(2-sulpho-5-amino-
phenylazo)-7-(4-sulphophenylazo)-8-naphthol-3,6-disulphonic
acid, l-amino-2-(2-sulpho-5-aminophenylazo)-7-(2-sulphophenyl-
azo)-8-naphthol-3,6-disulphonic acid and 1-amino-2-(2-sulpho-
5-aminophenylazo)-7-(2,5-disulphophenylazo)-8-naphthol-3,6-
disulphonic acid.
Equally valuable dyestuffs according to the invention
are obtained if, in the preparation of the abovementioned dis-
azo dyestuffs, the l-amino-8-naphthol-3,6-disulphonic acid
is replaced by l-amino-8-naphthol-4,6-disulphonic acid and if
the procedure is in other respects as described above.
Exam~le l9:
36.3 parts of bis-[~ -chloroethyl-sulphonyl)-ethyl]-


- 68 -

-~ Ref. 3062
7Z

.

amine hydrochloride are added, at O - 5, to a neutral solu-
tion of 80.8 parts of the dichlorotriazinyl compound of an
aminoxanthene which is described in German Offenlegungsschrift
2,442,839, Example 7, the mixture is warmed to 35 - 45 and
this temperature is maintained for ~ - 4 hours.
At the same time, the hydrogen chloride which is formed
is neutralised by adding 100 parts of 2 normal sodium hydrox-
ide solution dropwise and in portions, the pH value being kept
at 4.5 - 5.5. The reaction is complete when the pH value
remains constant. The blue-violet reactive dyestuff which
is prepared has the following structure:

C~2C~2N ~ N~ ~ N~ ~ N(CH2CH2s02c~2cH2c )2

~ S03H Cl
' ~
It is concentrated by evaporation in vacuo at 55 - 60 or is
precipitated with sodium chloride.
Similarly valuable reactive dyestuffs according to
the invention can be obtained if the dichlorotriaæinyl or
dibromotriazinyl compounds of aminoxanthenes which, in turn,
can be prepared in accordance with DOS 2,442,839 from the mono-
amines: taurine, N-ethyltaurine, aminoacetic acid, diethanol-
amine, 2- or 3- or 4-amino-benzene-sulphonic acid, l-amino-
benzene-2,4- or 2,5-disulphonic acid, 2-amino-toluene-4-
sulphonic acid, 3-amino-toluene-6-sulphonic acid or 4-amino-
toluene-2-sulphonic acid and from the diamines: 1,3-diamino-


- 69 -

` -~ Ref. 3062
~0~7172

benzene-sulphonic acid, 2,5-diamino-benzene-1,4-disulphonic
acid, 2,4-diamino-toluene-6-sulphonic acid, 2,6-diamino-
toluene-4-sulphonic acid, 4,4'-diamino-diphenyl-2,2'-disulphonic
acid, 4,4'-diaminostilbene-2,2'-disulphonic acid, 4,4'-
diamino-diphenylurea-2,2'-disulphonic acid or 2,6-diamino-
naphthalene-4,8-disulphonic acid, are employed as the starting
dyestuffs. The dyestuffs should contain at least two groups
which impart solubility,
Exam~le 20:
73,0 parts of the copper complex of the dyestuff 4-(2-
hydroxy-5-nitro-3-sulpho-phenyl-azo) 6-(5-dichlorotriazinyl-
amino-2-sulpho-phenyl-azo)-1,3-dihydroxybenzene are stirred in
700 parts of water at pH 6.5 and at about 10. 36.3 parts
of bis-[~ -chloroethyl-sulphonyl)-ethyl]-amine hydrochloride
are added to the mixture. The temperature is then raised
to 45 - 50. When the pH value has fallen to 3.8, 17
parts of sodium bicarbonate are added in the course of 4 - 5
hours in such a way that the pH value remains between 3.8 and
4.8. When the pH value is constant, it is adjusted to 7.0
with 2 normal sodium hydroxide solution and the resulting
dyestuff of the formula
S03~

2 ~ 0 - Cu- p
N--G~
0 ~ E ~ - N(CH2CH2S02cH2cH2cl)2

Cl
S03H

- 70 -




' . ~

~ Z Ref. 3062


is isolated by salting-out or spray-drying.
The copper complex which is employed as the starting
material can be obtained as follows: a diazo compound pre- -
pared from 23.4 parts of 4-nitro-2-aminophenol-6-sulphonic
acid is coupled with 11,0 parts of 1,3-dihydroxy-benzene at
0 - 5 and at pH 5.5 - 6.5. This monoazo dyestuff is con-
verted into the copper complex in acetic acid solution by
adding 25,0 parts of crystalline copper sulphate. The dye-
stuff i9 precipitated by salting-out with sodium chloride and
is filtered off and re-dissolved in water. It is then
coupled at 5 - 15 and with the addition of sodium bicarbonate, ~-
with the diazo compound prepared from 23.0 parts of 2-amino-
5-acetamino-benzene-sulphonic acid, to give the disazo dye-
stuff. The latter is heated at 80 with sodium hydroxide
solution and the acetyl group is split off. The dyestuff
obtained in this way is then reacted, at 0 - 5 and at p~ 6 -
6.5, with 18.5 parts of cyanuric chloride.
Similar valuable dyestuffs according to the invention
are obtained if the dyestuffs which follow are employed instead
of the copper complex dyestuff employed as the starting mat-
erial: the copper complex of 4-(2-hydroxy-5-sulpho-phenyl-
azo)-6-(5-dichlorotriazinylamino-2-sulpho-phenyl-azo)-1,3-
dihydroxybenzene, the 2:1 chromium complex of 4-(2-hydroxy-5-
sulpho-phenyl-azo)-6-(4-dichlorotriazinylamino-2-sulpho-
phenyl-azo)-1,3-dihydroxy-benzene, the copper complex of 4-(2-
hydroxy-3-chloro-5-sulpho-phenyl-azo)-6-(4-dichlorotriazinyl-
amino-2 sulpho-phenyl-azo)-1,3-dihydroxy-benzene, the 2:1cobalt
complex of 4-(2-hydroxy-6-nitro-4-sulpho-naphthyl-1-azo)-6-


- 71 -

-- Ref, 3062
1~717Z


(4-dichlorotriazinylamino-2,5-disulpho-phenyl-azo)-1,3-
dihydroxy-benzene and the copper complex of 4-(2-hydroxy-3,5-
disulpho-phenyl-azo)-6-(6-dichlorotriazinylamino-4,8-disulpho-
naphthyl-2-azo)-1,3-dihydroxy-benzene,
ExamPle 21:
Pre~aration of the startin~ d~estuff:
38.9 parts of the dyestuff obtained by coupling 6-
nitro-2-diazo-1-hydroxy-benzene-4-sulphonic acid and 2-
hydroxy-napthalene in a medium alkaline with sodium car-
bonate, are stirred in 200 parts of water at pH 8 and at a
temperature of 70 - 80. 67.9 parts of the chromium complex
compound of the azo dyestuff formed from 4-chloro-2-diazo-1-
hydroxy-benzene-6-sulphonic acid and 1-amino-8-hydroxy-
naphthalene-3,6-disulphonic acid, which contains 1 atom of
chromium for 1 molecule of dyestuff, are introduced into this
suspension, the pH value being kept between 7 and 9 by adding
æodium carbonate solution dropwise. After 20 minutes at
70 - 80, a dark blue solution has formed. The paper chro-
matogram shows that a single-substance mixed complex has been
formed. The mixed complex is acylated with 18.5 parts of
cyanuric chloride for one hour at 0 and at pH 6.5 - 7.5.
Pre~aration of the dyestuff accordin~ to the invention:
36.3 parts of bis-C~ -chloroethyl-sulphonyl)-ethyl]-
amine hydrochloride are added to the solution of the starting
dyestuff obtained in this way and the mixture is warmed to 50
in the course of ~0 minutes. mis temperature is maintained
for 4 hours. During this time the pH value is ~ept between
5.0 and 5.5 by adding 11.5 parts of sodium carbonate, When

- 72 -




,
.
, ~ ~ , .,
,
,

1~7172 Ref. 3062
. ~,

the pH value remains constant, it is adjusted to 7.0 with
dilute sodium hydroxide solution and the dyestuff of the form-

ula
_ ... .

~2'-~P3_.111-~3 1
0 ~ ¦ \ 0 NH ~ N(CH2CH2~02CH2cH2cl)2
o3~ =N~ ~
~-s03 5 Na+
Cl
J
is isolated by spray-drying.
ExamPle 22:
72.6 parts of bis-[~ chloroethyl-sulphonyl)-ethyl]-
amine hydrochloride are added to a suspension of 115.6 parts
of the bis-(dichlorotriazinyl) compound of bis-[6-(5-amino-2-
~sulpho-phenylazo)-5-hydroxy-7-sulpho-naphthyl-2]-amine. The
batch is warmed to 35-40. The pH value is kept at 4.5 - 5
by adding 200 partsof2normal sodium hydroxide solution in
portions. The reaction is complete when the pH value re-
mains constant. The orange-red reactive dyestuff is then
concentrated by evaporation in vacuo at 55 - 60 or is pre-
cipitated with sodium chloride. It has the following
structure:

-= Ref. 3062
~ 371~Z




~(ClCH2C~2S02cH2c~2)2~ ~ H
Cl ~ N=N ~

L Iso H 3 ~ 12 .~H

The bis-(dichloro-triazinyl) compound of bis-~6-(5-amino-2-
sulpho-phenyl-azo)-5-hydroxy-7-sulpho-2-naphthylj-amine
which is used as the starting material is obtained in the
following way: ~7.6 parts of 2,~-diamino-benzene-sulphonic
acid are acylated at 0 - 5 and at a pH value of 6 - 7 with
a suspension of 37.0 parts of cyanuric chloride. me resul-
ting 2-amino-4-(~,5-dichloro-2,4,6-triazinyl-amino)-benzene-
sulphonic acid is diazotised in the usual way and is coupled
at 0 - 5 while adding Z5 parts of sodium bicarbonate.
Similar valuable reactive dyestuffs according to the
lnvention are obtained if 2,5-diamino-benzene-sulphonic acid
is employed instead of 2,4-diamino-benzene-sulphonic acid in
the starting dyestuffs which are to be prepared.
In addition, bis-[5-hydroxy-7-sulpho-2-naphthyl]-amine
can be replaced by the following coupling components: bis-[5-
hydroxy-7-sulpho-2-naphthyl]-urea, bis-[5-hydroxy-7-sulpho-2-
naphthyl]-thiourea, bis-[8-hydroxy-6-sulpho- 2-naphthyl]-amine,
bis-[8-hydroxy-6 sulpho-2-naphthyl]-urea or bis-L8-hydroxy-6-
sulpho-2-naphthyl]-thiourea.
Example 23:
10 parts of woollen piece goods are introduced at 40C
into a dye liquor which contains, in 500 parts of water, 0.1

- 74 -




.

~ 717Z Re~. 3062

:

part of the dyestuff obtained in Example 8, 0.6 part of 30
per cent strength acetic acid, 0.5 part of anhydrous sodium
sulphate and 0.2 part of a surface-active auxiliary, and the
dye bath is heated to 70Cin the course of 20 minutes.
After 30 minutes at 70C,the temperature of the dye bath is
raised to 98 - 100Cin the course of 30 minutes and is kept
at this temperature for 60 minutes. The dyed material is
then rinsed with warm water and then with cold water and is
finally dried at 60 - 70C. A clear red shade which is dis-
tinguished by good fastness to light, wet processing and
perspiration, is obtained.
ExamPle 24:
A fabric composed of mercerised or caustic-shrunk cot-
ton is printed with the following printing ink:
30 g of the dyestuff prepared according to Example 6,
150 g of urea,
340 g of hot water,
450 g of an alginate thickener,
20 g of calcined sodium carbonate and
10 ~ of the sodium salt of m-nitrobenzenesulphonic acid.
1,000 g
After printing and drying, the goods are steamed for
approximately 5 minutes at 100 - 105C and are rinsed and
washed. A strong yellow print with very good fastness to
wet processing and light is obtained.
A similar deep print is obtained if the dyestuff is
fixed, not by steaming, but by dry heat, for example at 140 -
150C for 5 minutes.

~ 75 -




', . ..

Ref. 3062
10~717Z

The dyestuff can also be used in a two-phase printing
process. In this, the printing ink has the following com-
position:
30 g of the above dyestuff,
50 g of urea,
460 g of hot water,
450 g of an alginate thickener and
10 ~ of the sodium salt of m-nitrobenzenesulphonic acid.
l,ooo g
After printing and drying, the goods are padded with:
30 g of 38 Bé sodium hydroxide solution,
150 g of sodium carbonate,
50 g of potassium carbonate,
100 g of sodium chloride and
water, to give
1,000 ml
and are steamed immediately afterwards at 120 - 130C for
approximately 30 seconds.
If a liquor having a higher content of sodium hydrox-
ide (50 - 100 g/l) is used, the dyestuff can also be fixed by
the cold pad-batch method, that is to say by padding and storing
the printed goods at room temperature for 3 - 5 hours. The
so-called wet developing process is also possible using a
liquor of the same composition, In this case, the dyestuff ~`
is fixed in 5 - 10 seconds by the development liquor which is
heated to 95 - 105C.
Example 25:
30 parts of the dyestuff prepared according to Example

- 76 -

Ref, 3062
1087172


1 are dissolved in 1,000 parts of water. A cotton ~abric
is padded with this solution, squeezed out to give a liquor
pick-up of 80% and dried. It is then treated at 70C, for
~0 minutes, in a bath which contains 250 parts of calcined
sodium sulphate and 30 parts of 38 Bé sodium hydroxide solu-
tion dissolved in 1,000 parts of water. The dyeing is then
stored for 4 hours and is finished in the customary manner.
A clear, bluish-tinged red dyeing with excellent ~astness to
wet processing and light is obtained,
Examle 26:
~- 168 ml of water at 25C are initially placed in a dye
beaker with a capacity of 300 ml, which is placed in a water
bath which can be heated, 0,3 g of the dyestuff obtained
according to Example 1 is made into a smooth paste with
2 ml o~ cold water and 30 ml of hot water (70C) are added;
in the course thereof the dyestuff dissolves. The dyestuff
solution i8 added to the water which was initially taken and
10 g of cotton yarn are continually agitated in this
dye liquor, The temperature of the dye liquor is raised
to 70 - 80C in the course of 10 minutes, 20 g of sodium chlor-
ide and 6 g of sodium carbonate are added and dyeing is carried
out for 60 minutes, The liquor adhering is then removed
by squeezing out and the material is rinsed with cold and hot
water, The dyed material is then soaped for 20 minutes at
the boil, rinsed again and dried, A clear red dyeing with
outstanding ~astness to washing and light and good stability
against the action of chlorine, is obtained,


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