Note: Descriptions are shown in the official language in which they were submitted.
~1014~;2
The present invention relates to fibre-reactive azo dyes
of the formula
N - B - (SO3H)n
A-N=N ~ ¦
L ~ ~
wherein A is a residue of benzene or naphthalene, Y is methyl,
sulphomethyl, carboxyl or carbamoyl, B is hydrogen, an alkyl or
aryl radical, R is hydrogen or alkyl of 1 to 4 carbon atoms, X is
alkyl or alkoxy of 1 to 4 carbon atoms, carboxyl or halogen~ n is
a positive integer from 1 to 6 and m is 1 or 2, and A and B can
contain as further substituents alkyl groups of 1 to 4 carbon
atoms, alkoxy groups of 1 to 4 carbon atoms, acylamino groups of
1 to 6 carbon atoms, amino groups, the ureido, hydroxyl and car-
boxyl group and halogen atoms, and the phenylamino radical bonded
to the s-triazine ring can contain as further substituent at the
phenyl nucleus, in addition to and independently of X, an alkyl
radical of 1 to 4 carbon atoms, and, if m is 2, 'che substituents
R and X of both 2-fluoro-4-(2'-X-phenylamino)-s-triazin-6-yl-
N(R) radicals can be different and metal complexes of the fibre-
reactive azo dyes of the formula (1).
Examples of substituents on the benzene or naphthalene
residue A are methyl, ethyl and propyl radicals; methoxy,
-- 2 --
~,'' 1
ethoxy, propyloxy and isopropyloxy groups; acetylamino,
propionylamino and benzoylamino groups; -NH2~ methylamino and
ethylamino groups; and fluorine, chlorine and bromine atoms.
An alkyl radical B is in particular an unsubstituted
alkyl radical, for example methyl or ethyl; however, the alkyl
radicals can also be further substituted, for example by chlor-
ine, hydroxy, cyano and amino.
Preferably B is an aryl radical, in particular a phenyl
or naphthyl radical, which, in addition to S03H groups, can
contain for example the substituents cited above as examples
for the radical A. Suitable values for R as alkyl radicals of
1 to 4 carbon atoms are: methyl, ethyl, propyl, isopropyl,
butyl, isobutyl, sec-butyl and tert-butyl.
Suitable values for X as alkyl radicals of 1 to 4 carbon
atoms are: methyl, ethyl, propyl, isopropyl, butyl~ isobutyl,
sec-butyl and tert-butyl, and as alkoxy radicals of 1 to 4
carbon atoms: methoxy, ethoxy, propyloxy, isopropyloxy, butyl-
oxy, isobutyloxy, sec-butyloxy and tert-butyloxy. Halogen is
to be understood as meaning fluorine, chlorine and bromine.
Possible further substituents in addition to and independ-
ently of X which can be present at the phenyl nucleus of the
phenyl-
-- 3 --
al
~ 141Z
~...
amino radical bonded to the s-triazine ring are: methyl,
ethyl, propyl, isopropyl, butyl, isobutyl, sec -butyl and
~: tert -butyl.
~ .
~; The sulpho groups can be distributed at random among the
: :~ radicals A and B.
:~ ~ Preferred fibre-reactive azo dyes are those of the formula
(1), wherein m is 1 and the 2-fluoro-4-(2'-X-phenylamino)-s-
triazin-6-yl-N(R3 radLcal i.s bonded_to the.radiçal A._X iS=~
,-- , ~, ,, _ ~ , , , _ , . . _ ,, . , _ , _ _ _ . ., _ _ . . . _ _ _ _ ~
~rerera~ly methyl, meth_xy, carboxyl or chlorine.
i
~ 1 An important subgroup of fibre-reactive azo dyes of the formula
:: ~ (1) consists of those wherein A is a sulphophenyl radical, Y
.~ . is methyl or carboxyl, B is a phenyl or naphthyl radical which
;is unsubstituted or substituted by sulpho and chlorine, R is
: hydrogen and m is 1, and X and n are as defined in formula (1).
~ . ~
Useful fibre-reactive azo dyes of the formula (1) are for
: example the~fibre-reactive azo dye of the formula
. OH SO H
: ~ 1 3
¢~ 't; '~,rq~C~ ~
~ N SO3H
,. .
and that of the formula
i::: ~ .
4 -
- '
.
.. . , ' ,
. ' , ,, , ' .
, '
~ 4 1 2
OH SO~
C ~lr~ ~ ~ S03
N N / I ~ SO
COOH
.
The dyes of the formula (1) are fibre-reactive since they
contain a removable fluorine atom in the s-triazine radical.
By fibre-reactive compounds are meant those compounds which
are able to react with the hydroxyl groups of cellulose or
with the amino groups of natural or synthetic polyamides to
form covalent chemical bonds.
The manufacture of the fibre-reactive azo dyes of the formula
(1) consists in reacting a diazotised amino compound of the
formula
A-NH2 (2),
a coupling component of the formula
OH
N-~ (3)~
wherein A and B together contain 1 to 6 sulpho groups,
.. .... . . .. .
and. A_and/or B..contain a -N(R)H group,.l or.2.e.quival nt.s
of 2,4,6-trifluoro-s-triazine of the formula
-- 5 --
111~1412
CI-~
~,N
and 1 or 2 equivalents of identical or different aminobenzenes
of the formula
a ¦ 2 ~ - (5)
- X
by coupling and condensation in optional sequence to give a
fibre-reactive aæo dye of the formula (1).
The starting material is preferably an aminobenzene of the
formula (5), wherein X is methyl, methoxy, carboxyl or
chlorine.
In preferred embodiments of the above described process, the
starting compounds are compounds of the formulae (2) and (3)
wherein only A, but not B, contains a -N(R)H group.
A further preferred embodiment is that wherein the starting
materials are compounds of the formula (2), wherein A is a
sulphophenyl radical of the formula (3), in which Y is methyl
or carboxyl, and B is a phenyl or naphthyl radical which is un-
. substituted or substituted by sulpho and chlorine, whilst A
and B together contain 1 to 6 sulpho groups and A or B contains.
a -NH2 group, one equivalent of 2,4,6-trifluoro-s-triaæine of
... .
..
. . .........
4 12
the formula (4) and one equivalent of an aminobenzene of the
formula (5), wherein X is as defined in formula (1).
Since the sequence in which the above process steps are carried
out can vary and some, if appropriate, can be carried out
simultaneously, a number of different variants of the process
are possible. The starting materials to be used for each
partial reaction result from formula (1). In general, the re-
action is carried out stepwise in succession and the sequence
of the simple reactions of the individual reaction components
of:the formulae (2), (3), (4) and (5) can be freely chosen.
Important variants of the process are:
1) coupling a diazotised amino compound of the formula (2)
with a coupling component of the formula (3) to give an azo com-
pound, coDdensing this azo compound with 2,4,6-trifluoro-1,3,5-
triazine of the ~ormula (4) and condensing the primary conden-
:
sation~product thereby obtained with an aminobenzene of theformula (S) to give a fibre-reactive dye of the formula (l);
2) condensing a coupling component of the formula (3) with
2;,4,6-tri:fluoro-~1,3,5-triazine of the formula (4), condensing
the: primary condensation product thereby obtained with an
aminobenzene of the formula (5) and coupling the secondary
condensation product with a diazotised amino compound of the
formula (2) to give a fibre-reactive azo dye of the formula (1);
3) condensing a coupling component of the formula (3) with
:
2,4,6-trifluoro-1,3,5-triazine of the formula (4), coupling
- 7 -
.
:
.' . . ~ ,
.. , . . ~
.
.
11~141Z
the primary condensation thereby obtained with a diazotised
amino compound of the formula (2) and condensing the resultant
azo compound with an aminobenzene of the formula (5) to give
. a fibre-reactive azo dye of the formula (l);
~: 4) condensing an amino compound of the formula (2) with
2,4,6-trifluoro-s-triazine of the formula (4), condensing the
:
resultant primary condensation product with an aminobenzene
of the formula (5), diazotising the secondary condensation
:product and coupling it with a coupling component of the formula
:: (3) to give a fibre-reactive azo dye of the formula (1);
5) condensing an amino compound of the formula (2) with
.;2,4,6-trifluoro-s-triazine of the formula (4), diazotising the
~:
primary condensation product thereby obtained and coupling it
wlth a coupling component of the formula (3) and condensing
the;resultant azo compound with an aminobenzene of the formula
(S):to~give a fibre-reactive dye of the formula (l);
:6)i: coupling a diazotised amino compound of the formula (2)
with~a~coupling component of the formula (3) to give an azo
compound~condensing this azo compound with 2 equivalents of
2,4,6-trifluoro-s-triazine of the formula (4) and condensing
the resultant diprimary condensation product with 2 equivalents
of~an aminobenzene of the formula (5) to give a fibre-bi-
reactive azo dye of the formula (l);
i: :
~ ~ ~ 7) coupling a diazotised amino compound of the formula (2)
;
: with:a coupLing component of the formula (3) to give an azo
8 -
. .
.
llal4~2
compound and condensing this azo compound with 2 equivalents
of the primary condensation product of 2,4,6-trifluoro-s-tria-
zine of the formula (4) and an aminobenzene of the formula
(5) to give a fibre-bireactive azo dye of the ~ormula (1).
Examples of starting materials which can be used for the manu-
facture of the fibre-reactive azo dyes o~ the formula (1) are:
Amino compounds of the formula (22 (diazo components)
i-aminobenzene-2-, -3- and -4-sulphonic acid,
l-aminobenzene-2,4- and -2,5-disulphonic acid,
l-amino-4-methylbenzene-2-sulphonic acid,
l-amino-3-methylbenzene-6-sulphonic acid,
l-amino-6-methylbenzene-3- or -4-sulphonic acid,
l-amino-2,4-dimethylbenzene-6-sulphonic acid,
l-amino-2-carboxybenzene-4-sulphonic acid,
l-amino-4-carboxybenzene-2-sulphonic acid,
l-amino-4- or -5-chlorbenzene-2-sulphonic acid,
l-amino-6-chlorobenzene-3- or -4-sulphonic acid,
l-amino-3,4-dichlorobenzene-6-sulphonic acid,
l-amino-2,5-dichlorobenzene-4-sulphonic a~id,
l-amino-4-methyl-5-chlorobenzene-2-sulphonic acid,
l-amino-5-methyl-4-chlorobenzene-2-sulphonic acid,
l-amino-4- or -5-methoxybenzene-2-sulphonic acid,
l-amino-6-methoxybenzene-3- or -4-sulphonic acid,
l-amino-6-ethoxybenzene-3- or -4-sulphonic a id,
l-amino-2,4-dimethoxybenzene-6-sulphonic acid,
-. ,.- . -
.
1101412
l-amino-2,5-dimethoxybenzene-4-sulphonic acid,
1,4-diaminobenzene-2-sulphonic acid,
1,3-diaminobenzene-6-sulphonic acid,
1,4-diaminobenzene-2,5-disulphonic acid,
1,3-diaminobenzene-4,6-disulphonic acid,
l-amino-3-acetylaminobenzene-6-sulphonic acid,
l-amino-4-acetylaminobenzene-2-sulphonic acid,
l-amino-3-acetylamino-4-methylbenzene-6-sulphonic acid,
aminonaphthalene-2-, -4-, -5-, -6-, -7- or -8-sulphonic acid,
2-aminonaphthalene-1-, -5- or -6-sulphonic acid,
aminonaphthalene-3,6- or -5,7-disulphonic acid,
,
: : 2-aminonaphthalene-1,5-, -1,7-, -3,6-, -5,7-, -4,8- or
-6,8-disulphonic acid,
: ~ ;: l-aminonaphthalene-2,5,7-trisulphonic acid,
2-aminonaphthalene-1,5,7-, -3,6,8- or 4,6,8-trisulphonic acid,
hydroxy-2-aminobenzene-4-sulphonic acid,
~: ~ z ;l-hydroxy-2-aminobenzene-5-sulphonic acid,
,
l-hydroxy-2-aminobenzene-4,6-disulphonic acid,
hyd:roxy-2~-amino-4-acetylaminobenzene-6-sulphonic acid,
I-hydroxy-2-amino-6-acetylaminobenzene-4-sulphonic acid,
l-hydroxy-2-amino-4-chlorobenzene-5-sulphonic acid,
, ~ ~
l-hydroxy-2-amino-4-methylsulphonyl-benzene,
l-amino-2-hydroxy-6-nitronaphthalene-4-sulphonic acid,
2-amino-1-hydroxynaphthalene-4,8-disulphonic acid.
'
- 1 0 -
~ ~ .
` 1 ~0 14 1 ~
- Coupling components of the formula (3)
3-methyl-5-pyrazolone,
5-pyrazolone-3-carboxylic acid,
l-phenyl-3-sulphomethyl-5-pyrazolone,
1-(4'-sulphophenyl)-3-methyl-5-pyraæolone,
1-(4'-sulphophenyl)-5-pyrazolone-3-carboxylic acid,
1-(3'-sulphophenyl)-3-methyl-5-pyrazolone,
1-(3'-sulphophenyl)-5-pyrazolone-3-carboxylic acid,
1-(2',5'-disulphophenyl)-3-methyl-5-pyrazolone,
1-(2'-, 3'- or 4'-chlorophenyl)-3-methyl-5-pyrazolone,
1-(2'-chloro-4'-sulphophenyl)-3-me~hyl-5-pyrazolone,
1-(2'-chloro-5'-sulphophenyl)-3-methyl-5-pyrazolone,
1-(2'-sulpho-4'-chlorophenyl)-3-methyl-5-pyrazolone,
1-(2',5'-dichloro-4'-sulphophenyl)-3-methyl-5-pyrazolone,
1-(2'-methyl-4'-sulphophenyl)-3-methyl-5-pyrazolone,
. 1-(2'-methyl-4'-sulphophenyl)-5-pyrazolone-3-carboxylic acid,
1-(6'-chloro-2'-methyl-4'-sulphophenyl)-3-methyl-5-pyrazolone,
1-(4',8'-disulphonaphthyl[2'])-3-methyl-5-pyrazolone,
1-(4',8'-disulphonaphthyl[2'])-S-pyrazolone-3-carboxylic acid,
1-(5',7'-disulphonaphthyl[2'])-3-methyl-5-pyrazolone,
1-(5',7'-disulphonaphthyl~2'])-5-pyrazolone-3-carboxylic acid,
1-(4',6',8'-trisulphonaphthyl-[2'~)-3-methyl-5-pyrazolone,
1-(4',6',8'-trisulphonaphthyl-[2'])-5-pyrazolone-3-carboxylic
acid,
1-(6l-amino-4',8'-disulphonaphthyl[2'])-3-methyl-5-pyrazolone,
- 11 -
.. ~ ..... .. . . . . , .. ... ~ ., . , .. , . .. ... . . .. . ... . .. _ . .g, . ..
-
, :.
4 1 2
1-(3'- or 4l-aminophenyl)-3-methyl-5-pyrazolone,
1-(3'-aminophenyl)-5-pyrazolone-3-carboxylic acid,
1-(4'-amino-2'-sulphophenyl)-3-methyl-5-pyrazolone,
1-(4'-amino-2'-sulphophenyl)-5-pyrazolone-3-carboxylic acid,
2~4,6-Trifluoro-1,3L~triazine (cyanuric fluoride~ of the
formula (4~
Aminobenzenes of the formula (5)
l-amino-2-methylbenzene,
l-amino-2-ethylbenzene,
l-amino-2-propylbenzene,
l-amino-2-methoxybenzene,
l-amino-2-ethoxybenzene,
l-amino-2-carboxybenzene,
l-amino-2-chlorobenzene,
l-amino-2-bromobenzene,
l-amino-2-fluorobenzene,
l-amino-2,4-dimethylbenzene,
l-amino-2,5-dimethylbenzene.
The diazotisation of the amino compounds of the formula (2) is
usually effected by treatment with nitrous acid in an aqueous
mineral acid solution at low temperature, and the coupling with
the coupling components of the formula (3) is carried out at
weakly acid or neutral to weakly alkaline pH values.
- 12 -
.. , . .. .. . . . . . . . .. . . ~ . .. .. .... . . .
~ 2
The condensation reactions of the 2,4,6-trifluoro-1,3,5-tria-
zine with the amino compounds of the formula (2), the coupling
components of the formula (3) and the aminobenzenes of the
formula (5) are carried out preferably in aqueous solution
or suspension, at low temperature and at weakly acid or neut-
ral to weakly alkaline pH values. Advantageously, the hydrogen
fluoride set free during the condensation is neutralised con-
tinuously by the addition of aqueous alkali hydroxides,
carbonates or bicarbonates.
If the benzene or naphthalene residue A contains a complex-
forming group in the ortho-position ~o the azo group, for
example a hydroxyl or carboxyl group, it is also possible to
manufacture metal complexes of the fibre-reactive azo dyes of
the formula (1) by treating azo compounds obtained by the above
described process with metal donors, before or after the con-
densation with fluorine-s-triazine. The copper complexes are of
particular interest. They are obtained by treating corres-
ponding azo compounds, wherein A is a benzene or naphthalene ra-
dic~l which contains a complex-forming group in the ortho-
position to the azo group, with copper donors before or, if
desired, also after the acylation with the fluorine-1,3,5-
triazine.
A suitable method of coppering is not only that described
above in which an o,o'-dihydroxyazo compound is used as
starting material for the complexing, but also oxidative copper-
- 13 -
.. , . . ., . . . .... ., . ,. .. . . , ., . .... .... . ~ , . ... . . ... .. . w
14~l;2
ing, in which the hydroxyl group necessary for the complexing
is not introduced into the naphthalene nucleus until during
the coppering reaction by simultaneous treatment with an oxi-
dant. Instead of a l-hydroxy-2-amino-naphthalene-4,8-disul-
phonic acid, the corresponding 2-amino-naphthalene-4,8-disul-
phonic acid is used for example in this case as diazo com-
ponent.
However, to obtain the copper-complexes of the compounds of the
formula (1) it is also possible to use diazo components which
contain an alkoxy group instead of a hydroxyl group in the
l-position of a naphthalene nucleus, in. particular the methoxy
group, which is converted into the hydroxyl group under suitable
reaction conditions during the coppering reaction by splitting
off the alkyl radical.
As copper donors it is possbile to use for example salts which
contain copper as cation, for example copper sulphate and copper
acetate. In many cases it is advantageous to use complex copper
compounds, for example in the form of copper-am~ine complexes,such
as copper tetramminesulphat~ from copper sulphate and ammonia,
pyridine or monoethanolamine, or in the form of compounds which
contain copper bound as a complex, for example complex copper
compounds of the alkali salts of aliphatic aminocarboxylic
acids or hydroxycarboxylic acids, such as of glycine, of lactic
acid and, in particular, of tartaric acid, such as sodium
copper tartrate. - 14 -
... ..
Q1412
The treatment with the copper donors can be carried out bymethods which are known per se, for example at room temperature,
if easily metallisable starting compounds are used, or if
simultaneously with the metallising it is necessary to effect
dealkylation,by heating to temperatures between 50 and 120C
in an open vessel, for example with reflux cooling or optionally
in a closed vessel under pressure, the pH conditions being
provided by the nature of the chosen metallising procedure:
for example an acid coppering with coppe`r sulphate and an
alkaline coppering with copper tetramminesulphate.If desired,
solvents, for example alcohol, dimethyl formamide etc., can
also be added during the metallising. In the oxidative coppering,
an oxidant, in particular hydrogen peroxide, is added to the
reaction mixture, and the reaction is in other respects carried
out in the described manner.
The fibre-reactive azo dyes of the formula (l) are distinguished
by a pronounced reactivity and a high degree of fixation. They
are suitable for dyeing and printing a very wide variety ofma-
terials, such as silk, leather, wool, polyamide and polyurethane
fibres, and especially cellulosic materials of fibrous structure,
such as linen, cellulose, regenerated cellulose, and in parti-
cular cotton. They are suitable both for the exhaustion process
and for dyeing by the pad-dyeing process, in which the goods
are impregnated with aqueous and, if appropriate, also with
salt-containing dye solutions, and the dyes are fixed after
treatment with alkali or in the presence of alkali, optionally
- 15 -
... ..... . . ..
. . .
.
. . ~ ' ' .
110~12
with the application of heat.
They are also suitable for printing, in particular on cotton,
and also for printing nitrogen-containing fibres, for example
wool, silk or blends containing wool.
It is advisable to rinse the dyeings and prints thoroughly
with cold and hot water, if appropriate with the addition of
an agent which acts as a dispersant and promotes the diffusion
of non-fixed dye.
In the following Examples, the parts and percentages are by
weight.
- 16 -
... .... , ., . ,, , . .. . . . .,,, , . .. , ., . . ~ .
141~
E x a m p 1 e
14 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise
at 0 to 5C in the course of 30 minutes to an aqueous solution
containing 65 parts of the trisodium salt of 1-(2'-naphthyl)-
3-methyl~4-(5"-aminophenylazo)-pyrazolone-(5)-2",4',8'-tri-
sulphonic acid. When the addition is complete, the free amino
group of the starting product is no longer detectable. During
the entire duration of the dropwise addtition the pH of the
solution is kept between 6.5 and 7.5 by the simultaneous
addition of 2N sodium hydroxide solution. Then 11 parts of 2-
aminotoluene are added, the temperature is slowly raised to
20C and the pH value is kept continously at 7 during the
condensation. The dye of the formula
¢! ~ o~ c_~S0~ 3
~ . CH3 S03
is salted out of the resultant clear solution by sprinkling
in potassium chloride, isolated by filtration, dried and
ground, giving a yellow dye powder which dyes wool in fast
yellow shades.
Further useful dyes with similar colouristic properties are
obtained by repeating the procedure of this Example using the
aminopyrazolone dyes of column I of Table 1 and carrying out
the second condensation with the amines listed in column II.
- 18 -
.. . . . ...
412
, . . .
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g ~ o ~ X
t~ ~ o o :~
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11~141~
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- 20 -
11~31~12
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g
o U~
N _I ~ ~ ~ H
H p~ ~ ..
C~,
. O J ~ I
, ,,
O .~ td NN ~ N ~ rC t~
. ~ ~d U ~
O ~ p~rl
U O ~ O~rl O O O
~ O ~C.J p U ~ O
o
N E ~ ~E ~; E C E~ Q~
~d ~ ~ ~ U~ Otd O ~d
,1 I ~ l ~,1 1 ~ I .~ I
~ ~ ~ ~C ~ Q. ~ ~ ~ u~
.
r~ o~ ~ O ,~
~1 ~ ~ C~
.
- 21 -
4 12
E x a m p 1 e 2
66 parts of the intermediate of the formula
H03S 0 - Cu -0
C ~ I ~ N-N ~ ~ 03H
C~l3 NH
3 2
obtained by coupling l-hydroxy-2-amino-4-acetylaminobenzene-6-
sulphonic acid to 1-(4',8'-disulphonaphthyl[2'])-3-methyl-5-
pyrazolone, subsequently saponifying the acetylamino group and
complexing with a copper donor, are dissolved at 0C and pH
7 in 700 parts of water. This pH value is maintained by further
addition of sodium hydroxide solution following the dropwise
addition of 14 parts of 2,4,6-trifluoro-1,3,5-triazine. When
the condensation is complete (detectable by the absence of free
amino groups), 13,3 parts of 1-amino-2-chlorobenzene are added.
The temperature is raised to 35C and the pH is kept at 8.5
with further sodium hydroxide solution. The dye is precipitated
with sodium chloride, collected by suction filtration, dried
and ground. It dyes cotton in very fast reddish brown shades.
Further brown dyes with similar properties are obtained by con-
densing the copper complex dyes of column I of Table 2 with
equivalent parts of 2,4,6-trifluoro-1,3,5-triazine and then
with the amines listed in column II in accordance with the parti-
culars of this Example.
- 22 -
41~
_
~ ~ , ,
,Q
o o ~ o
h O P~ .--1 0
C ~ ~ U
~ l l l l l l
_~ h
O ~
~1 ~1 O O ~ O Q) O ~J O al o ~
~ ~D E3 a) E3 N E N Ei N ~ N ~3 N
~1
Ia~I~ Ia~Ia) Ia) Ia
N~--I ,CI-1 ,~~1 ~ ~1 ~ r-l
. ' __ _
I I
~J ~ O
P~ N I
C ~tll tY)
.LI ~ ~ _~ aJ h
O X~\ X ~ ~ ~_ :~ h X
I r~ 1 0 1 ~ p~, J t~ ~1
C~
I E~ I u o ~ E~
O~_ O ~1 O~ I O
~- ~I v , ~
~ ~ I~ I tO O~ V O O O ~ I
a) ~ I N ~ C O
1:~ ~ o c,.~/ ~
O rC `' ~--'~ h ~ 1 N --1 0 ~'
R~ C4 Q~ X ~ N
Ei ~3 O a) o Q) O C~ O O ~ C~
O O ~ ~ I X r~: Q X rl ~ ~
S~ ~ ~ OCL O O Irl a) c~ ~4 a~ '~:1 'Ql aJ ~ ~, ~J
~J ~ ~ t ~ ~ ~ I I ~ I
~ ~ O~ O ,~ ~ o., ~ ~ o. - U~ o.~ _ I
q~ ~) N u~ N V ~ ~
c~ ~ ~,1 I ~ I ,~ O I ~ O ^ ~ O ^ I ~1
~:: ~1 - h - $~1 - ~ V - I V - ~ V - ~ ~1
a~ ~1 CL ~ ~~ P~
_~ td ::~ `~ - X
t~ ~ O I II I I I ~ I O ~ `J O
E~ ~o U~
P~
. ~ ~ ~1
p~ ~~ V ~ V
~ I ~ V~r~
o
V O V O V O
O td ~ C
N I Q~ I Cl. I Q~
td ~ ~1~ ~ ~) ,_
I
P~ O U~ O ~ O U~
Q ~ I ~ ~ I ~ ~ I
O ~
I ~ 1
~; O
CL, I N O I N O I N O
. ~ P~
U ~ X ~ ~ X
O, o ~9 0 ,9 U~ O ,9 U~
h I `-- h I `-- h I --'
O ~ O ~ 0 ~0 0
N
~_1 I E3 t I E3
~1 ~ t~
~___ . _ .
.
C~l ~ ~ U~
- 23 -
I U . O ~
e c e
~ ~ 3 ~
~ ~ o
a ; ~ ~ 2 e ~ O
~O ~ . ~
H L e
~ Ç~
O ~
~ @.~ x~
o~ ~
__
.~ . r~
- 24 -
-
11~141~:
E x a m p 1 e 3
26.8 parts of 1,4-diaminobenzene-2,5-disulphonic acid are dis-
solved in 300 parts of water at pH 7 and 0C. With efficient
stirring, 14 parts of 2,4,6-trifluoro-1,3,5-triazine are added
dropwise while simultaneously keeping the pH between 6.5 and 7
by the addition of 2N sodium hydroxide solution and the
temperature at 0C by the addition of ice. When 1 equivalent
of sodium hydro~ide solution has been consumed, 12.1 parts of
l-amino-2-ethylbenzene are tipped in. The temperature is raised
to 40C and the pH is kept at 8 with a further equivalent of
sodium hydroxide solution. When the condensation is complete,
the batch is cooled to 0 to 5C, acidified wi~h 30 parts of
concentrated hydrochloric acid,and diazotisation is effected
by the dropwise addition of an aqueous solution of 7 parts of
sodium nitrite. This suspension of the diazo compound is added
to a neutral solution of 29 parts of 1-(2'-chloro-5'-sulpho-
phenyl)-3-methyl-5-pyrazolone to which 30 parts of sodium
carbonate have been added. When the coupling is complete, the
pH is adjusted to 7 and the dye of the formula
¢ ~ ~ IN ~ N=N _ ~ H-C C-NH ~
3 ~C CH2CH3
S03H CH3 F
- 25 -
. . . . . . .
.
,
'. - ' :. " ~ .
1~;14~2
is precipitated by addition of a 1:1 mixture of potassium and
sodium chloride, collected by suction filtration, dried and
ground, giving a yellow dye powder which dyes cotton in fast
reddish yellow shades.
Dyes with similar properties are obtained by condensing 2,4,6-
trifluoro-1,3,5-triazine with the diaminobenzenesulphonic acids
of column I of Table 3 and subsequently with the amines listed
in column II, diazotising the secondary condensation products
and coupling the resultant diazonium compounds in accordance
with the particulars of this Example with the coupling com-
ponents listed in column III.
- 26 -
- - - .....
.
. `
.
.
: ` ,
.
41Z
_ _
, ~
.~ ,_
I ~d I I I I I ~ ~1
o ~ ~ ~ o ~ o P~ :~
1 ~ ~ P~
o o
~, U ~ ,1 C ,~
~ ~ o ~ u~
o ~ o o
~ , ~ ,, , o , ~ ~J ~
O -- -- ~ - N ~ -- ~ O
O I ~ I ,~
~1 O (11 0 ~1 ~1 ~ 1 0 au
bO S~
~ o I o ~ I a) o
~
I ~,c o a~ I o o - u~
C).. tJ ~ ~ 3 ~ ~ 01 ~1 N Ll'~ 1
:~I .--1 a) I o o I ~ x ~ ~1 0 t~
-- ~ -- ,~ N - :~ O -- P . N S~
C.) ~ O ~ ~ tl~
'~1 h
I .~ o I
Q. N ~ u~
a~ ~
a) N ~) ~U N
N ~: N N ~:
a) rQ a) a) .o
0 ~C
P~ O' ~ ~ O
. ~ O ~
E~ U t~
I I
rl C~l ~ C~l
a~ ~ o o o o o
.
E~
l l l l l
. ~ 1
.,~ ~ I
U~
C`l `J C~
~rl N N N
1~ E~i S~
~rl ~
~ O _ O C~
.~
. ~ ~-~1
I I Q ~ ~
_ .. ___
27 -
Z
_ _
~ U~
H O ~ O
rl
I~
~ I O^ I rl
C~ ~ ~X
I ~ I ~ O
~1 ~ ~,1:)
. .
~J N ~
~ O
~ U ~ ~ ~
O O O
t~
E~ ~ ~
C UU
.,1 0~ 0
~ .~
.~ U ~ ~
g
--
lZ
E x a m p 1 e 4
26.B parts of 1,3-diaminobenzene-4,6-disulphonic acid are
added to 400 parts of water at pH 7 and, after cooling to
0C, 14 parts of 2,4,6-trifluoro-1,3,4-triazine are added
dropwise, while keeping the pH at 7 by adding sodium hydroxide
solution. When the condensation is complete, the condensation
mixture is acidified with 30 parts of concentrated hydro-
chloric acid and diazotisation is effected by adding 7 parts
of sodium nitrite. Simultaneously, 32 parts of 1-(2',5'-di-
chloro-4'-sulphophenyl)-3-methyl-5-pyrazolone are dissolved
in 300 parts of water at pH 8. The diazo suspension is intro-
duced into this solution and the pH is kept between 8 and 9
by the addition of sodium hydroxide solution. When the reac-
tion components can no longer be detected, 12.3 parts of 1-
amino-2-m~thoxybenzene are added dropwise and the temperature
is simultaneously raised to 20 to 30C. Meantime, the pH is
kept at 8 by the further addition of sodium hydroxide solution.
When the condensation is complete, the dye is salted out and
collected by suction filtration. The residue is dried and
ground, giving a yellow dyestuff powder. The dye has the
formula pl OH
~H-C~ ~c-NH
H03S I ~ N N
Cl CH3 H03S S03H ~?C/ OCH3
F
- 29 -
' : ' '
: :
and it dyes cellulose in very fast greenish yellow shades.
Further dyes are obtained by condensing 2,4,6-trifluoro-
1,3,5-triazine with a diaminobenzenesulphonic acid of column ~
of Table 4 in accordance with the above procedure, diazotising
the resultant condensation product and coupling it with a
coupling component of column II, and finally condensing the
azo compound thereby obtained with the amine of column III.
- 30 -
12
. . . ~
a~
N a~ N ~ N al N
~:: N ~ N N tL) ,C: N ~::
0 1~ N Q~
ra a
~ ~ X ~
O S~O P~ :~ ~ O ~ O
~ oQ ~ .~
C~
U c~v P~
C~l C~3 ~ ~ ~ ~ C~l ~ C~l
O O O O O O O O O
a a ~ a a a ~ ~ a
e
.
~,~ ~ ~,
.
o ~ o ~
N P~ ( CJ
I ~d ~ O C~
I O ~ ~) N O~1 a) O ~ ~C
. ~ O
~ ~ O ~ ~ o~,n I
o ~ a) ~ I ~ ~ ~ o ~ ~ ~ o
O P~ O U~ I O I u~ O O N u~ 30 t~ p~
N ~ ~1 1 ~1.1:~ U~I N ,~:: td I N
~d ~ O - P P~
S~ N `J ~: ~1 ~1 `;t ~ ~ ~ Lr')
P, a~
o ~ ~o o~ ~o I o Q~ o
I ~ ~ ~ ~ I rl O ~ ~
~ ~ ~ C~ .C I~ ~O U~ ~ I O U~ ~ ~ ~ o
E-l I ~ I JJ ~ I E~ r/ I I r-l ~1 1 1 0 rl r-l
--13 U~ U I ~l ~ N 3 0
~, 0 1 ~ ~ CO ~ C) ~ 1~ ,~: C~ p~ 00 CiJ 0 N
I ~ I ~1 ^ ~ I ~ ~` ~ I ~ ^ ~ I td
S c~
I I a~ I ~ I ~ ; I I t~ I I I Ll'~ v I I
U3 ~
N ~ ~D -
I I I t
N rl N rl N rl N
~ U
a
. ' .~ ~ ~I ~0 U ~ V ~0
H ~3
t~
~ ~ O ~ O ~ O ~-rl
~ ~ rl O
I ~ I ~ 1 3 I tl~
~.,1 ^.,~ ^-rl ^ 3
r~l '~:) ~1 ~ ~1 ~1 ~1 U~
.. I
- 31 -
` 1 lQ ~
E x a m p 1 e 5
249.2 parts of 1-(4'-amino-2'-sulphophenyl)-4-(5"-amino-2"-
sulphophenylazo)-5-pyrazolone-3-carboxylic acid (prepared by
diazotisation of l-amino-3-acetylaminobenzene-6-sulphonic acid,
coupling to l-(4'-amino-2'-sulphophenyl)-5-pyrazolone-3-car-
boxylic acid and subsequent saponification of the acetylamino
group) are dissolved in 1000 parts of water at pH 7 by adding
sodium hydroxide solution. After cooling to 0C, 135 parts
of 2,4,6-trifluoro-1,3,5-triazine are added dropwise, while
keeping the pH constant by further addition of sodium hydroxide.
When no more free amino groups can be detected, 107.2 parts
of l-amino-2-methylbenzene are added dropwise. The temperature
is rapidly raised to 40C and the pH is kept at 8 by the
further addition of sodium hydroxide solution. The dye of the
fonnula
,N ~ N ~ NH C~N\c NH
¢ ~ ~ NH-C C-NH ~ ~ N=N ~ ~ N N
CH N N ~S03H IOOH S03H F CH3
is salted out, filtered off, dried and ground. It is a dry
powder which dyes cotton in fast yellow shades.
Further bireactive dyes with similar properties are obtained
by condensing the diaminoazo dyes of column I of Table 5 with
2,4,6-trifluoro-1,3,5-triazine and subsequently with the amines
listed in column II in accordance with the particulars of this
ExampleO
- 32 -
. .
412
H. O a) O O
¢ I S I
~1.~ ~,Q
I I I
.~ S I
~ ~ ~( N
_
I I
~ ~ rl
u~ Cd
a~ ~
E~
~
O O O
X
O ~ ,~
,~ N
~ ~ U~
H I I I I al
O ~, ~ u~ ~) ,C~ Cd
N ~ 0~ 1:
. ~ N ~) N N
. . ~
~1 a~ ~1 U~ ~ ^-rl
~ ~ ~ I O `J ~
r~ O rl ~ ~ I ~
rl O O
I ~ I 1:~ E3 C
E ~
_ _ ~ .
__ ~
- 33 -
1~141Z
E x a m p 1 e 6
26.8 parts of 1,4-diaminobenzene-2,5~disulphonic acid are
diazotised and coupled to 26.9 parts of 1-(4'-amino-2'-sul-
phophenyl~-3-methyl-5-pyrazolone A suspension of 47.2 parts
of the condensation product of 1 equivalent of 2,4,6-trifluoro-
1,3,5-triazine and 1 equivalent of 1-amino-2,5-dimethylbenz-
ene in 250 parts of water is tipped into a neutral solution
of the above intermediate in 500 parts of water. The pH is
kept between 7.5 and 8 by the addition of sodium hydroxide
solution. The batch is then stirred at room temperature until
free amino groups can no longer be detected. The solution is
then concentrated and the residue ground, giving a dye of the
formula
CH so3~ OH ICH3
~ "N~ ~ N ~ -N~l-C C-NH - ~ ~
~NH-C C-NH~N=N~ J N N ~IJ
CH3 ~C ~ S03H CH3 ' 3
which dyes cotton in reddish yellow shades of excellent fast-
ness. Bireactive dyes with similar properties are obtained by
condensing the diaminoazo dyes listed in column I of Table 6
in accordance with the particulars of this Example with the
primary condensation product of 2,4,6-trifluoro-1,3,5-triazine
and the amines of column II.
4~2
__ _ . _ _
~ a)
a)
~ O ~ O
k ~
CN ~`1 ~ C~l
l l l l
~0 0~
~ 1 rl a)
E
I I a~
,
O O O ~
~ 1 rl I rl
_ - - ~::
`J ~ O .
I V I I O ~ :~
1` 1` P` ~, e .
'Cl ~ ~ ~ I ~
r~ Xrl .
o O c)
t~
O
~d O C~ O O E I
E-~ ,c~ N N
0~ d
C~ ~1
O:~ O
~:5 U~
rl Orl Or-l ~ N I
O `l:) N ~ N ~ CN
N I 1~) I t~) I ~ O
t~ Ln ~1 ~ 11 ~ ~1 ,C~
O ^ P~ 0 .-1
~ ~ C~
Ei o u~ ~ E
~ ~ t
.~ 0
N ~--I N :~ N ~ ~ O
~ O J
Q~
0~ 0 ~ O~
~1 0 ~
~ 0-~
~1 ~rl ~rl I ~ I ~
O O
I u~
I c~
c~
_
_ ~
,
- 35 -
,2
Dyeing Procedure I
2 Parts of the dye obtained according to Example 1 are dis-
solved in 100 parts of water while adding 0.5 part of sodium
m-nitrobenzenesulphonate. A cotton fabric is impregnated with
the resultant solution to a liquor pick-up of 75% and then
- dried.
The fabric is then impregnated with a warm solution of 20C
which contains, per litre, S g of sodium hydroxide and 300 g
of sodium chloride, and squeezed out to a pick-up of 75%. The
dyeing is steamed for 30 seconds at 100 to 101C, rinsed,
soaped for a quarter of an hour in a 0.3% boiling solution of
a non-ionic detergent, rlnsed and dried.
,
Dyeing Proced~re II
2 Parts of the dye obtained according to Example 1 are dis-
801ved in 100 parts o~ water. The solution is added to 1900
parts of cold water, 60 parts of sodium chloride are added
~nd 100 parts of a cotton fabric are put into this dyebath.
The temperature is raised to 40QC and 40 parts of calcined~
sodium carbonate and another 60 parts of sodium chloride are
~dded after 30 minutes. The tempera~ure is kept for 30 minutes
~t 40C. The dyeing is rinsed and then soaped for 15 minutes
in a 0,3% boiling solution of a non-ionic detergent, rinsed
and dried.
- 36 -
