~ 4
-- 1 --
1-11902/=
Reactive dyes, processes for their manufacture and use ~hereof
The present invention provides reactive dyes of the formula
D - N - C C - N ~ $1)
Rl N~ ~N R2
F X
wherein D is the radical of an organic dye which contains sulfo groups,
Rl is hydrogen or Cl-C4alkyl, R2 is hydrogen, methyl or ethyl, X is
a radical of the formula -S02CH2CH2Cl, -S02CH=C~2, -S02C~l2CH2~S03H,
H CH OP0 H or -N(R3)S02CH2CH20S03H, and 3
or ethyl, and the benzene or naphthalene radical can contain further
substituents in addition to X.
In the reactive dyes of the formula (1), the radical D is
in particular the radical of a dye of the mono- or polyazo, metal
complex azo, anthraquinone, phthalocyanine, formazane, azomethine,
nitroaryl, dioxazine, phenazine or stilbene series.
Preferred reactive dyes are those of formula (1), wherein
D is the radical of a mono- or disazo dye.
As alkyl of 1 to 4 carbon atoms, the subst~tuent Rl in
formula (1) is methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
sec-butyl and tert-butyl.
If the radical bonded through the -N(R~) bridge member to
the s-triazine ring is a naphthalene radical, it can be bonded in the
a- or ~-position.
In addition to containing one or more sulfo groups, the
radical D in formula (1) can contain further substituents, for exam-
ple alkyl groups of 1 to 4 carbon atoms, such as methyl, ethyl, propyl,
isopropyl and butyl, alkoxy groups of 1 to 4 carbon ato~sl such as
methoxy, ethoxy, propoxy, isopropoxy and butoxy, acylamino groups of
1 to 6 carbon atoms, such as acetylamino, propionylamino and benzoyl-
amino, halogen, such as fluorine, chlorine and bromine, nitro7 cyano,
trifluoromethyl, sulfamoyl, carbamoyl, ureido, hydroxyl, carboxyl,
and sulfomethyl.
In addition to X, the benzene or naphthalene radical in
formula (1) can contain-eTg~ the following further substituents:
Cl-C4alkyl, Cl-C4alkoxy, halogen, such as fluorine, chlorine and bro-
mine, nitro, hydroxyl, carboxyl and sulfo.
Preferred reactive dyes of the formula (1) are those wherein
Rl is hydrogen, methyl or ethyl, and each of R2 and R3 is a hydrogen
atom..
An important class of reactive dyes comprises those of the
formula
HO
A-N=N~ (S03H)m
~ ~ CO~}, ~ C C-~
~C~
~2), F
wherein A is a benaene or naphthalene radical, m is 1 or ~, n is O or
1 and p is O or 1, ~hile the benzene or naphthalene radical A and the
benzene radical B can contain further substituents and X is as defi-
ned for formula (1).
Further eligible substituents in the benzene or naphthalene
-- 3 --
radical A and the benzene radical B are the same as those named as
possible substituents in the radical D in the definition of formuha
(1) .
If the radical D or A contains complex forming groups, such
as hydroxyl, carboxy-l, amino and sulfo groups, it is also possible to
obtain the heavv metal complexes of the reactive dyes of the formulae
(1) and (2).
A valuable reactive dye of the class characterised by formu-
la (2) is that of the formula
SO H ~N ~ ~
03 ~ ~ C' 502CH2CH20S3
S03H
~3) ,
The reactive dyes of the formula (1~ are obtained by conden-
sing in any order, 2,4,6-trifluoro-s-triazine of the formula
~N~
F - C C - F
N N (4) ,
~C'
F
an organic dye of the formula
D - NH
Rl (5)
which contains sulfo groups, or a primary product thereof, and an
amine of the formula
-
3~
-- 4 --
HN ~
R2 ~ (6)
to produce a reactive dye of the formula (1), and, if primary products
are used, converting these latter into the desired end dyes of the for-
mula (1).
Organic dyes of the formula (5) which contain sulfo groups
are, in particular, those wherein D is the radical of a dye of the
mono- or polyazo, metal complex a7-o, anthraquinone, phthalocyanine,
formazane, azomethine, ni~roaryl, dioxazine, phenazine or stilbene
series.
Preferred starting materials are organic dyes of the formula
(5) which contain sulfo groups,in which D is the radical of a mono~ or
disazo dye.
As the individual process steps described above can be car~..^.
ried out in varying sequence, and, if desired, in some cases also
simultaneously, different variants of the process are possible.
In general, the reaction is carried out stepwise in succes-
sion and the sequence of the simple reactions between the individual
reaction components of the formulae (4), (5) and (6) can be freely
chosen.
Important processes variants for obtaining the reactive dyes
of the formula (l) comprise
1) condensing 2,4,6-trifluoro-s-triazine of the formu1a (4) with an
organic dye of the formula (5) which contains sulfo groups and conden-
sing the primary condensation product with.an amine of the formula (6);
~,
. . . . . .. .
3'~
2) condensing 2,4,6-trifluoro-s-triazine of the formula t4) with an
amine of the formula (6) and condensing the primary condensation pro-
duct with an organic dye of the formula (5) which contains sulfo groups.
In a modification of the above process, the reactive dyes of
the formula (1), wherein D is the radical of an organic dye which is
composed of t~o or more components ~nd contains sulfo groups, can be ob-
tained by condensing one component of the dye of the formula (5) which
contains a -~ group~, a- 2,4,6-trifluoro-s-triazineof the formula (4)
and an aminobenzene of the formula (6), and, in any step of the process,
reacting the condensation product with the o~her component or compo-
nents of the dye of the formula (5) to produce a reactive dye of the
formula (1).
Exa~ples of such organic dyes which are composed of two or
more components are: monoazo, disazo, trisazo, tetraazo, metal com-
plex azo,formazane and azomethine dyes,
The above described process modification is chiefly of impor-
tance for the manufacture of reactive dyes of the formula (1)~ wherein
D is the radical of an azo dye which contains sulfo groups. In these
dyesl that portion of the azo dyestuff radical to which the s~triazine
radical is bonded can be either the radical of the diazo component or
the radical of the coupling component. This possibility gives rise to
two variants of the above described modification of the process.
The first of these two variants consists in condensing a
diazo component which contains a -~ group with 2,~,6-trifluoro-s-
triazine of the ormula (4~, diazotising the resulting condensattonproduct and coupling the diazo Gompound to a coupling component, and
- reacting the resulting azo compound, before or af~er the coupling, with an amine of the fo~mula (6).
-- 6 --
The second variant cansists in condensing a coupling compo-
nent which contains a -~1 group with 2,4,6-trifluoro-s-triazine of the
formula (4) and coupling a diazotised diazo component to the condensa-
tion product and reacting the resulting azo compound, before or after
the coupling, with an amine of the formula ~6).
In this process variant, it is possible to obtain reactive
dyes of the formula (1) which contain two reactive s-triazine radicals
by condensing a diazo componentwhich contains a ~ ~ group with a 2,4,6-
trifluoro-s-triazine of the formula (4), and also condensing a coupling
component which contains a - ~ group with a 2,4,6~trifluoro-s-~rianzine
I
of the for~ula ~4) and diazotising the condensation product of the dia-
zo component and coupling the diazonium compound to the condensation
product of the coupling component and reacting theresulting azo com-
pound, before or after the coupling, with an amine of the formula (6).
Reactive dyes, which contain two or more reactive s-triazine
radicals can also be obtained by condensing organic dyes of the for-
mula (5) which contain sulfo groups and which contain further - ~
groups in the radical D, with a corresponding amount of the 2,4,6-tri
fluoro-s~triazine of the formula (4), so that two or mores-triazine
radicals are introduced into the dye molecule.
A preferred embodiment of the process for the manufacture
of the reactive dyes of the formula (1) comprises the use of organic
dyes of the formula (5) which contain sulfo groups, wherein D is the
radical of a mono- or disazo dye, as starting materials, or condensing
diazo components and/or coupling components which contain a -N(Rl)H
group with the 2,4,6-trifluoro-s-triazine of the formula (4), and
subsequently,or after the further condensation with the
.
. .
-- 7 --
amine of the formula (6), obtaining the dye by coupling with the other
component or other components of the mono- or disazo dye respe~tively.
A further preferred embodiment is that wherein the starting
materials are organic dyes of the formula (5) which contain sulfo
groups, wherein Rl is hydrogen, methyl or ethy-l, and amines of the
formula (6), wherein each of R2 and R3 is a hydrogen atom.
The preferred reactive dyes of the formula (2) are obtained
by reacting, in any order, a diazotised amino compound of the formu~a
A - NH2 (~)
a coupling component of the formula
HO
(S03H)~ (8)
~ CO ~ } - ~H ~ ~I
2,4,6-trifluoro-s-triazine of the formula (4) and an amine of the for-
muIa
2 ~ (9)
by coupling and condensation, to produce a reactive dye of the formula
(2).
The most important process variants for obtaining the reac-
tive dyes of the formula (2) com~rise
1) coupling a diazotised amino compound of the formula (7) with a cou-
pling component of the formula (8) to produce an azo compound of the
formula
HO
A-~=N ~ (~3H)m (10)
~ ~ } - ~ ~ H
condensing this azo compound with 2,4,6-trifluoro-1,3,5-triazine-of
the formula (4) and condensing the primary condensation product wi~h
an amine of the formula (9) to produce a reactive dye of the formula
(2);
2) condensing a coupling component of the formula (8) with 2,4,6-tri-
fluoro-1,3,5-triazine of the formula (4), condensing tbe primary con-
densation product with an amine of the formula (9) and coupling the
secondary condensation product with a diazotised amino compound of the
formula (7) to produce a reactive dye of the formula (2);
3) condensing a coupling component of the formula (8) with 2,4,6-tri-
fluoro-1,3,5-triazine of the formula (4), coupling a diazotised amino
compound of the formula (7) to the primary condensation product and
condensing the resulting azo compound wi-th an amine of the formllla (9)
to produce a reactive dye of the formula (2).
If the end reactive dyes of the formula (1) and (2) contain
complex forming groups, they can subsequently be reacted with heavy
metal donors.
The~particularly valuable reactive dye of the for~ula (3) is
preferably obtained by process variant 2) by condensing 1-amino-8~hy-
droxynaphthalene-3,6-disulfonic acid with cyanuric fluoride, condensing
the primary condensation product with l-aminobenzene-3-~-sulfatoethyl-
sulfone, and coupling diazotised 2-aminonaphthalene-1,5-disulfonicacid
to the secondary condensation product.
,,
': '
.
.
- 9 ~ 34
As starti.ng materials for the manufacture of the dyes of
the formula (1) there may be mentioned:
a) 2,4,6-Trifluoro-s-tria~.ine (cyanuric fluoride) of the formula
(4)
b) Organic dyes of the formula (5) which contain sulfo groups
1. Monoazo compounds of the fonmula
OH
!dO35 ~ - NHRl (Il) ,
wherein Dl is an at most bicyclic aryl radical which contains no azo
groups and -NHR groups, Rl is hydrogen or Cl-C4 alkyl and the -NHR
group is preferably bonded to the 5-, 6-, 7- or 8-position of the
naphthalene nucleus, and which additionally can contain a sulfonic
acid group in the 5- or 6-position of the naphthalene nucleus.
Dl can be a radical of the naphthalene or benzene series
which does not contain any azo substituents, for example a stilbene,
diphenyl, benzthiazolylphenyl or diphenylamlno radical. In this class,
attention is also drawn to the related dyes in which the -NHR group,
instead of being bonded to the naphthalene nucleus, is bonded to a
benzoylamino or anilino group which is bonded to the 5-1 6-, 7- or
8-position of the naphthalene nucleus.
Particularly valuable starting dyes are those. wherein Dl is
a sulfonated phenyl or naphthyl radical, especially those which con-
tain a -SO3H group in the ortho-position to the azo bond. The phenyl
radical can be further substituted, for example by halogen atoms, such
as chlorine atoms, alkyl radicals, such as methyl, acylamino groups,
such as acetylamino and alkoxy radicals, such as methoxy.
2. Disazo compounds of the formula (11), wherein Dl is a radi-
cal of the azobenzene, azonaphthalene or phenylazonaphthalene series
A_ . ~
3~
-- 10 --
and the naphthalene nucleus is substituted by the -N~Rl group and, if
desired, by sulfonic acid, as in class 1.
3, Monoazo compounds of the formula
D - N - N ~ ~ N~Rl (12) ,
wherein Dl is an at most bicyclic aryl radical, as described in class
1, and is preferably a disulfonaphthyl radical or a stilbene radical,
Rl is as defined above, and the benzene nucleus can contain further
substituents, such as halogen atoms or alkyl, alkoxy, carboxylic acid,
ureido and acylamino groups.
4. Monoazo or diazo compounds of the formula
H N Dl N (13)
Rl ,
wherein Dl is an arylene radical, for example a radical of the azo-
benzene, azonaphthalene or phenylazonaphthalene series or, preferably,
an at most bicyclic arylene radical of the benzene or naphthalene
series and K is the radical of a naphtholsulfonic acid or the radical
of an enolised or enolisable ketomethylene compound (such as an aceto-
acetarylide or a 5-pyrazolone) with the OH group in the ortho-position
to ~he azo group, and Rl has the above meaning. Dl represents prefer-
ably a radical of the benzene series which contains a sulfonic acid
group.
5. Monoazo or diazo compounds of the formula
Dl - N = N ~ Kl N~DRl
wherein Dl is a radical of the types defined for Dl in classes 1 and
2 abo~e and Kl is the radical of an enolisable ketomethylene compound
(such as an acetoacetarylide or a 5-pyrazolone) with the OH group in
the ortho-position to the azo group.
~\ ~
6. The metal complex compounds, for example the copper complexes,
chromium complexes and cobalt complexes of the formulae (11) to (14),
wherein each of Dl, K and Kl has the indicated meaning, and furthermore
a metallisable group (for example a hydroxyl, lower alkoxy or carbo-
xylic acid group) is present in the ortho-position to the azo group
Examples
Class 1:
6-amino-l-hydroxy-2-(27-sulfophenylazo)-naphthalene-3-sulfo-
nic acid, 6-methylamino-1-hydroxy-2-(4'-acetylamino-2'-sulfophenylazo)-
naphthalene-3-sulfonic acid,
8-amino-1-hydroxy-2-(2'-sulfophenylazo)-naphthalene-3,6-disulfonic acid,
8-amino-1-hydroxy-2-(4'-chloro-2'.-sulfophenylazo)-naphthalene-3,5-di-
sulfonic acid,
7-amino-2-(2',5'-disulfophenylazo)-1-hydroxynaphthalene-3-sulfonic acid,
7-methylamino-2-(2'-sulfophenylazo)-1 hydroxynaphthalene-3-sulfonic
acid,
7-methylamino-2-(4'-methoxy-2' sulfophenylazo)-l-hydroxy-naphthalene-
3-sulfonic acid,
~-~3'-aminobenzoylamino)-l-hydroxy-2-(2'-sulfophenylazo)-naphthalene-
3,6-disulfonic acid,
8-amino-1-hydroxy-2,2'-azonaphthalene-1',3',S',6-tetrasulfonic acid,
8-amino-1-hydroxy-2,2'-azonaphthalene-1',3',5'-trisulfonic acid,
6-amino-1-hydroxy-2,2'-azonaphthalene-1',3',5'-trisulfonic.acid,
6-methylamino-1-hydroxy-2,2'-azonaphthalene-1',3',5'-trisulfonic acid,
7-amino-1-hydroxy-2.,2'-azonaphthalene-1',3-disulfonic acid,
8~amino-1-hydroxy-2-(4'-hydroxy-3'-carboxyphenylazo)-naphthalene-3,6-
disulfonic acid and
6-amino-1-hydroxy-2-(4'-hydroxy-3'-carboxyphenylaæo)-naphthalene-3,5-
disulfonic acid.
- 12 -
Class 2:
8-amino-1-hydroxy-2-[4'-(2"-sulfophenylazo)-2'-methoxy-S'-methylphenyl-
azo]-naphthalene-3,6-disulfonic acid,
8-amino-1-hydroxy-2-~4!-(4" ~ethoxyphenylazo)-2'-carboxyphenylazo]-
naphthalene-3,6-disulfonic acid,
8-amino-1-hydroxy-2-[4'-(2"-hydroxy-3",6"-disulfo-1"-naphthylazo)-2'-
carboxyphenylazo]-naphthalene-3,6-disulfonic acid,
4,4'-bis-(8"-amino~ hydroxy-3",6"-disulfo-2"-naphthylazo)-3,3'di-
methoxydiphenyl and
6-amino-1-hydroxy-2-~4'-(2"-sulfophenylazo)-2'-methoxy-5'-methylphenyl-
azo]-naphthalene-3,5-disulfonic acid.
Class 3:
2-(4'-amino-2'-methylp~enylazo)-naphthalene-4,8-disulfonic acid7
2-(4'-amino-2'-acetylaminophenylazo)-naphthalene-5,7-disulfonic acid,
4-nitro-4'-(4"-methylaminophenylazo)-stilbene-2,2'-disulfonic acid,
4-nitro-4'-(4"-amino-2"-methyl-5"-methoxy-phenylazo)-stilbene-2,2'-
disulfonic acid,
4-amino-4'-(4"-methoxyphenylazo)-stilbene-2,2'-disulfonic acid, and
4-amino-2-methylazobenzene-2',5'-disulfonic acid.
Class 4:
1-(2',5'-dichloro-4'-sulfophenyl)-3-methyl-4-(3"-amino-4"-sulfophenyl-
azo)-5-pyrazolone,
1-(4'-sulfophenyl)-3-carboxy-4-(4'-amino-3"-sulfophenylazo)-5-pyrazo-
lone,l-(2'~methyl-5'-sulfophenyl)-3-methyl-4-(4"-amino-3"-sulfophenyl-
azo)-5-pyrazolone,
1-(2'-sulfophenyl)-3-methyl-4-(3"-amino-4"-sulfophenylazo)-5-pyrazolo-
ne, 4-amino-4' (3"-methyl-1"-phenyl-4"-pyrazol-5"-onylazo)-stilbene-
2,2'-disulfonic acid,
4-amino-4'-(2"-hydroxy-3",6"-disulfo-1"-naphthylazo)-stilbene-2,2'-di-
sulfonic acid,
8-acetylamino-1-hydroxy-2-(3'-amino-4'-sulfophenylazo~-naphthalene-
3,6-disulfonic acid,
7-(3'-sulfophenylamino)-1-hydroxy 2-(4'-amino-2'-carboxyphenylazo)-
34
- 13 ~
naphthalene-3-sulfonic acid,
8-phenylamino-1-hydroxy 2-`(4"-amino-2'-sulfophenylazo)-naphthalene-3,6-
disulfonic acid and
6-acetylamino-1-hydroxy-2-(5'-amino-2'-sulfophenylazo)-naphthalene-3-
sulfonic acid.
Class 5:
1-(3'-aminophenyl)-3-methyl-4-(2'~5'-disulfophenyl-azo)-S-pyrazolone,
1-(3'-aminophenyl)-3-carboxy-4-(2'-carboxy-4'-sulfophenyl-azo)-5-
pyrazolone,
4-amino-4'-[3't-methyl-4"-(2"',5"'-disulfophenylazo)-1"-pyrazol-5"-
onyl]-stilbene-2,2'-disulfonic acid and
1-(3'-aminophènyl)-3-carboxy-4-[4"-(2"', 5"'-disulfo~henylazo)-2"-
methoxy-5"-methylphenylazo]-5-pyrazolone.
C~ass 6:
The copper complex of 8-amino-1-hydroxy-2-(2'-hydroxy-5"-sulfophenyl-
azo)-naphthalene-3,6-disulfonic acid,
the copper complex of 6-amino-1-hydroxy-2-:(2'-hydroxy-5'-sulfophenyl-
azo)-naphthalene-3-sulfonic acid,
the copper complex of 6-amino-1-hydroxy-2-(2'-hydroxy-5'-sulfophenyl-
azo)-naphthalene-3,5-disulfonic acid,
the copper complex of 8-amino-1-hydroxy-2(2'-hydroxy-3'-chloro-5'-
sulfophenylazo)-naphthalene-3,6-disulfonic acid,
the copper complex of 6-methylamino-1-hydroxy-2-(2'-carboxy-S'-sulfo-
phenylazo)-naphthalene-3-sulfonic acid,
the copper complex of 8-amino-1-hydroxy-2-[4'-~2"-suIfophenylazo)-2'-
methoxy-5'-methylphenylazo]-napthalene-3,6-disulfonic acid,
the copper complex of 6-amino-1-hydroxy-2-[4'-(2",5"-disulfophenyl-
azo)-2'-methoxy-S'-methyl~henylazo]-naphthalene-3,5-disulfonic acid,
the copper complex of l-(3'-amino-4'-sulfophenyl)-3-methyl-4-~4"~(2"'-
5"'-disulfophenylazo)-2"-methoxy-5"-methylphenylazo]-5-pyrazolone,
the copper complex of 7-(4'-amino-3'-sulfoanilino)-1-hydroxy-2-
~
- 14 -
.
(2"',5"'-disulfophenylazo)-2"-methoxy-5"~methylphenylazo]-naphthalene-
3-sulfonic acid,
the copper complex of 6-(4'-amino-3'-sulfoanilino)-1-hydroxy-2-(2"-
carboxyphenylazo)-naphthalene-3-sulfonic acid,
the 1,2-chromiùm complex of 7-amino-6'-nitro-1,2'-dihydroxy-2,1'-
azonaphthalene-3,4-disulfonic acid,
the 1,2-chromium complex of 6-amino-1-hydroxy-2-(2'-carboxyphenylazo)-
naphthalene-3-sulfonic acid,
the 1,2-chromium complex of 8-amino-1-hydroxy-2-(4'-nitro-2'-hydroxy-
phenylazo)-naphthalene-3,6-disulfonic acid,
the 1,2-cobalt complex of 6-(4'-amino-3'-sulfoanilino)-1-hydroxy-2-
(5"-chloro-2'-hydroxyphenylazo)-naphthalene-3-sulfonic acid,
the 1,2-chromium complex of 1~(3'-amino-4'-sulfophenyl)-3-methy1-4-
(2"-hydroxy-4"-sulfo-1"-naphthylazo)-5-pyrazolone,
the 1,2-chromium complex of 7-(4'-sulfoanilino)-l~hydroxy-2-~4"-amino-
2"-carboxyphenylazo)-naphthalene-3-sulfonic acid~
.. . ..
.
Particularly important azo dyes which can be used for the
production of thereaction dyes of the formula (1) are the azo dyes of
the formulae
(S03H)o_3 ,.,
N = N - K
~ : ~
'i " (15) ,
~ _.
)H
H; Ol.H3; i~H-aCYl pH N (Rl )H
(HO3S )0~ N = ~ ~ (S03H) 1-3
and
34
- 15 -
; 3; CH3; ~H-acyl ,~(Rl)H
(H035) ~ ~ ~ ~ ~ (503H)o 3
(17) H3; NH-acyl
wherein K is the radical of a coupling component of the benzene,
naphthalene or heterocyclic ser~es, acyl is a low molecular aliphatic
~; acyl ~adical of notmore than 3 carbon atoms or an aromatic radical of
~- not more than 8 carbon a~oms and Rl i5 as defined for formula (1), and
the metal complex azo dyes of the formulae
A~ Me 9 N ~ (18)
)0 3 .~ : 1' .xj N -
H~OH, H; Cl; NO2 (S03H)1_3
N02
: and (S03H)0_2
I ,D Cu--,0
= N ~NH2 ( or ~;IH-ac~l )
~J (S03H)1_3
(19),
~Rl)H
wherein R and acyl are as defined in the formulae (15), (16) and (17)
and Me r~presents Cu, Cr or Co.
7. ~nthraquinone compounts which ccntain a group of the formu-
la -NHRl~ wherein Rl has the above meaning, bonded to an alkylamino
or arylamino group, which is Itself bonded to ~he -position of the
anthraquinone nucleus, in particular of the formula
(20)
~IH-Z ' ~
- 16 -
wherein theanthraquinonenucleus can contain an additional sulfonic
acid group in the 5-, 6-, 7- or 8-position and Z' is a bridge member
which is preferably a divalent radical of the benzene series, for
example a phenylene~ diphenylene or 4,4'-stilbene or azobenzene radi-
cal. Preferably Z' should contain one sulfonic acid graup for each
benzene ring present.
Examples
l-amino-4-(4'-aminoanilino)-anthraquinone-2,3'-disulfonic acid and the
corresponding 2,3', 5-, 2,3', 6- and 2,3', 7-trisulfonic acids, l-amino-
4-(4"-amino-4'-benzoylaminoaniline)-anthraquinone-2,3'-disulphonic
acid and the corresponding 2,3'5~~risulfonic acid, 1-amino-4-~4-'-(4"-
aminophenylazo)-anilino]-anthraquinone-2,2",5-trisulfonic acid, l-amino-
4-(4'-amino-3'-carboxyanilino~-anthraquinone-2,5-disulfonic acid~ 1-
amino-4-(3'-aminoanilino)-anthraquinone-2,4',5-trisulfonic acid and
the corresponding 2,4-disulfonic acid, 1-amino-4-['-(4"-aminophenyl)-
anilino]-anthraquinone-2,3",5-erisulfonic acid, l-amino 4-(4'-methyl.--
amino)-anilino-anthraquinone~2,3'-disulfonic ~cld and the correspon-
ding 2,3',5-trisulfonic acid, 1-amino-4-(4'-n-butylamino)-anilino-
anthraquinone-2,3'-disulfonic acid, 1-amino-4-(4'-methylamino-3'-
carboxyanilino)-anthraquinone-2-sulfonic acid, 1-amino-4-(3'-~-
hydroxyethylamino)-anilinoanthraquinone-2,5-disulfonic acid, 1-(4'-
aminoanilino)-anthraquinone-213'-disulfonic acid and 1-amino-4-(4'-
amino-2'-methoxyan.ilino)-anthraquinone-2,3'-disulfonic acid.
8. Phthalocyanine compounds of the formula
Pc ~ (SO2- ~ ` (21) ,
~ ( So2~H- Z ~~ )m
wherein Pc denotes a phthalocyanine nucleus., preferably copper phthalo-
cyanine,~ is -OH and/or -~H2, Z' is a bridge member9 preferably an
aliphatic, cycloaliphatic or aromatic bridge, and each af n and m is
1~ 2 or 3 and can be identical or different, provided that the sum of
n ~ m is not greater than 4.
, : ':
'
34
The dye compounds of the phthalocyanine series which can be
used as starting materials in the process of the invention are prefera-
bly metal-containfng phthalocyanines, such as copper phthalocyanines,
which contain at least one waterwsolubilising group, such as a sulfonic
acid group, and at least one group of the formula -NHRl, wherein Rl
has the above meaning. The -NE~l group or groups can be bonded direct
or through a divalent bridge to the benzene rings of the phthalocyan-
~ne nucleus,for example through a -phenylen-, -CO-phenylene-, -SO2-
phenylene-, -NH phenylene-, -S-phenylene-, -O-phenylene, -CH2S-pheny-
lene-, -CH20-phenylene-, -CH2-phenylene-, -SCH2-phenylene-, -SO2CH2-
phenylene-, -S02-NR-phenylene-, -CH2-, -S02NR-arylene, -NRCO-phenylene-,
-NRS02-phenylene, -S020-phenylene-, -CH2-, CH2NR-phenylene-, -CH2NH-
CO-phenylene-, -S02NR-alkylene-, -CH2NR-alkylene-, -CONR-phenylene-,
-CONR-arylene-, -SO2- or -CO- bridge. In the above divalent bridge
members, R is hydrogen alkyl or cycloalkyl, arylene denotes a divalent
aromatic radical which is unsubstituted or substituted, for example by
halogen, alkyl or alkoxy, and wherein the terminal bonds may be
attached to identical or different nuclei, and alkylene denotes a di-
valent aliphatic radical which can include heteroatomss such as ni-:
trogen, in the chain of atoms, for example the radical -CH2CH2-NH-CH2-
CH2-.
As examples of such divale~t aromatic radicals, which are referred to
as arylene, there may be mentioned:
aromatic nuclei, for example a benzene, naphthalene, acridine and car-
bazole nucleus, which can carry further substituents, and radicals o
the formula
~ ~ (~2)
wherein the benzene rings can carry further substituents and -D- deno-
tes a bridging group, for example -CH=CH-~ -NH-, -S-, -O-, -SO2-,
-NO-N-, -N~N-, -NH-CO-NH-CO-NH-, -O-CH2CH20- or
N N
~ 3)
-C C~
,
- 18 -
Examples
~ . .
3-(3'-amino-4'-sulfophenyl)-sulfamyl-copper phthalocyanine-
tri-3-sulfonic acid,
di-4-(3'-amino-4'-sulfophenyl)-sulfamyl-copper phthalocyanine-di-4-
sulfonic acid,
3-(3'-aminophenylsulfamyl)-3-sulfamyl-copper phthalocyanine-di-3-sul-
fonic acid,
copper phthalocyanine-4-N-(4-amino-3~sulfophenyl)-sulfonamide-4',4",
4"'-trisulfon;c acid,
cobalt phthalocyanine-4-4'-di-N-(4'-amino-4'-sulfophenyl)-carboxamide-
4",4"'-dicarboxylic acid, and
copper-4-(4'-amino-3'-sulfobenzoyl)-phthalocyanine.
Mixtures of phthalocyanines~can also be used. For example, a mi~ture
of approximately equal parts of copper phthalocyanine-N-(4-amino-3-
sulfophenyl)-su~fonamide-tr~sulfonic acid and copper phthalocyanine-di-
N-(4-amino-3-sulfophenyl)-sulfonamide-disulfonic acid can be used.
9. Nitro dyes of the formula
o2N-D-N-Q (24)1
wherein D is a naphthalene or benzene nucleus which can be further
substituted, the nitrogen atom N is in the ortho-position to the
nitro group, Z is a hydrogen atom or an unsubstituted or subs-tituted
hydrocarbon radical and Q is a hydrogen atom or an organic radical --
bonded to the nitrogen through a carbon atom, and wherein Q and Z are
not both hydrogen atoms, and Q can be bonded to Z, if Z is a hydro-
carbon radical, or can be bonded to D in the ortho-position to the
nitrogen atom N to form a heterocyclic ring, and which contain at
least one group of the formula -NHRl, wherein Rl has the above meaning,
in particular nitro dyes of the formula
~- NH-B-NHR (2~), ~
N02
:'
-- 19 --
wherein V and B are monocyclic aryl nuclei and the nitro group in V is
the ortho-position to the NH group.
Example
4-Amino-2'nitro-diphenylamine-3,4'-disulf~nic acid.
9. Metal complexes of formazane dyes of the formula
N=N-A-Yl _ ¦ rRll
C~ C / - t ~! l (n = 1 o~ 2) (26) ,
~ 8--Y2 n
wherein Q is an organic radical~ a nitro or cyano groùp, A and B are
radicals of diazo components of the benzene, naphthalene or hetero-
cyclic series and each of Yl and Y2 is a substituent which is bound
in the ortho-position to the azo group and which is able to form a
complex with a heavy metal, and Rl has the indica~ed meaning. The
radical Q is especially a radical of the benzene series, such as phe-
nyl or sulfophenyl, or a low molecular alkyl group, such as a methyl
group, a low molecular alkanoyl group, a low molecular, preferably
Cl-C4-carbalkoxy group, a benzoyl group or a heterocyclic radical,
and A and B are preferably phenyl radicals which are substituted by
sulfo, sulfonamido or alkylsulfonyl groups. Suitable substituents Yl
and Y2 are above all the hydroxyl and carboxyl groups. Suitable heavy
metals are copper, chromium, cobalt and nickel.
Examples
the copper complex of 2'-carboxy-2"-hydroxy-3"-amino-1,3,5-triphenyl-
formaæane-4'-5",3"'-trisulfonic acid,
the copper complex of 2',2"-dihydroxy-3'-amino-5'-methylsulfonyl-1,3,5-
triphenyl-3",5",4"'-trisulfonic acid,
the copper complex of 2'-carboxy-4'-amino-2"-hydroxy-1~3,5-triphenyl-
formazane-3",5",2"'-trisulfonic acid,
,
$~ 4
- 20 -
the copper complex of 2'-hydroxy-2"-carboxy-4"'-amino-1,3,5-triphenyl-
formazane-4'-4"-disulfonic acid,
the copper complex of 2',2"-dihydroxy-S"-amino-l~S-diphenyl-3-methyl-
formazane-S',3"-disulfonic acid,
the copper complex of 2',2"-dihydroxy-5'-amino-1,3,5-triphenylforma-
zane-3'-3"-5"-trisulfonic acid,
the copper complex of 2'-carboxy-3'-amino-2"-hydroxy-3"'(1""-phenyl-
3""-methyl-pyrazol-S""-onyl-4""-azo)-1,3,5-triphenylformazane-3",5",
2"",5""-tetrasulfonic acld,
the nickel complex of 2',2"-~icarboxy-1,5-diphenyl-3-(m-aminobenzoyl)-
formazane-4'-4"-disulfonic acid.
~ he following diazo and coupling components are particularly
suitable for the manufacture of the prefèrred reactive dyes of the
formula (1), wherein D is the radical of an azo dye:
~iazo components:
aminobenzene, l-amino-2-, -3- or -4-methylbenzene,
l-amino-2-, -3- or -4-methoxybenzene,
l-amino-2-, -3- or -4-chlorobenzene,
l-amino-2,5-dichlorobenzene, 1-amino-2,5-dimethylbenzene
l-amino-3-methyl-6-methoxybenzene,
l-amino-2-methoxy-4-nitrobenzene, 4-aminodiphenyl,
l-aminobenzene-2-, -3- or -4-carboxylic acid,
2-aminodiphenylether, 1-aminobenzene-2-, -3- or -4-sulfonamide~
-N-methylamide, -N-ethylamide, -~,N-dimethylamide or -N,N-diethylamide,
dehjdrothio-p-toluidine-sulfonic acid,
l-amino-3-trefluoromethyl-6-sulfonic acid,l-amino-3- or -4-nitroben-
zene7 1-amino-3- or -4-acetylaminobenzene,
l-aminoben~ene-2-, -3- or -4-sulfonic acid,
l-aminobenzene-2,4- and -2,5-disulfonic acid, 1-amino-4-methylbenzene-
2-sulfonic acid, 1-amino-3-methylbenzene-6-sulfonic acid, 1-amino-6-
methylbenzene-3- or -4-sulfonic acid, 1-amino-2-carboxybenzene-4-sul-
fonic acid, l-amino-4-carboxybenzene-2-sulfonic acid, 1-amino-4- or
-5-chlorobenzene-2-sulfonic acid, 1-amino-6-chlorobenzene-3- or -4-
sulfonic acid, l-amino-3,4-dichlorobenzene-6-sulfonic acid, l-amino-
2,5-dichlorobenzene-6-sulfonic acid, 1-amino-2,5-dichlorobenzene-4-
- 21 ~
sulfonic acid, l-amino-4-methyl-5-chlorobenzene~2-sulfonic acid, 1-
amino-5-methyl-4-chlorobenzene-2-sulfonic acid, l-amino-4- or -5-metho-
xybenzene-2-sulfonic acid, 1-amino-6-methoxybenzene-3- or -4-sulfonic
acid, l-amino-6-ethoxybenzene-3- or -4-sulfonic acid, 1-amino-2,4-di-
methoxybenzene-6-sulfonic acid, 1-amino-2,5-dimethoxybenzene-4-sulfo-
nic acid, l-amino-3-acetylaminobenzene-6-sulfonic acid, 1-amino-4-ace-
tylaminobenzene-2-sulfonic acid, 1-amino-3-acetylamino-4-methylbenzene-
6-sulfonic acid, 2-amino-1-methylbenzene-3,5-disulfonic acid, l-amino-
4-methoxybenzene-2,5-disul~onic acid, 1,4-diaminobenzene-2,5-disulfo-
nic acid, l-amino-3- or -4-nitrobenzene-6-sulfonic acid, l-aminonaphtha-
lene, 2-aminonaphthalene, 1-aminonaphthalene-2-, -4-, -5-, -6-, -7- or
-8-sulfonic acid,2-aminonaphthalene-1-, -5-, -6- or-8-sulfonic acid,
l-aminonaphthalene-3,6- or -5,7-disulfonic acid, 2-aminonaphthalene-
1,5-, -1,7-, -3,6-, -5,7-, -4,ô- or -6,8-disulfonic acid, l-aminonaph-
thalene-2,5,7-trisulfonic acid, 2-aminonaphthalene-1,5,7-, 3,6,8- or
-4,6,8-t~isulfonic acid, 1-hydroxy-2-aminobenzene-4-sulfonic acid,
l-hydroxy-2-aminobenzene-5-sulfonic acid, 1-hydroxy-2-aminobenzene-
4,6-disulfonic acid~ 1-hydroxy-2-amino-4-acetylaminobenzene-6-sulfonic
acid, l-hydroxy-2-amino-6-acetylaminobenzene-4-sulfonic acid, l-hydro-
xy-2-amino-4-chlorobenzene-5-sulfonic acid, 1-hydroxy-2-amino-4-methyl-
sulfonyl-benzene, l-amino-2-hydroxy-6-nitronaphthalene-4-sul~onic acid,
2-amino-1-hydroxynaphthalene-4,8-disulfonic acid, 4-aminoazobenzene-
3,4'-disulfonic acid, 3-methoxy-4-amino-6-methylazobenzene-2',4'-di-
sulfonic acid; 3-methoxy-4-amino-6-methylazobenzene-2l,5'-disulfonic
acid. --
Coupling components-
phenol, l-hydroxy-3- or -4-methylbenzene, 1-hydroxybenzene-4-~ulfonic
acid, l-hydroxynaphthalene, 2-hydroxynaphthalene, 2-hydroxynaphthalene-
6- or -7-sulfonic acid, 2-hydroxynaphthalene-3,6- or -6,3-disulfonic
acid, l-hydroxynaphthalene-4-sulfonic acid, 1-hydroxynaphthalene-4,6-
or -4,7-disulfonic acid, 1-amino-3-methylbenzene, 1-amino-2 methoxy-
5-me~hylbenzene, 1-amino-2,5-dimethylbenzene, 3-aminophenylurea, l-ami-
no-3-acetylaminobenzene, 1-amino-3-hydroxyacetylaminobenzene, 1,3-di~
'
aminobenzene-4-sulfonic acid, 1-aminonaphthalene-6- or -8-suIfonic
acid, l-amino-2-methoxynaphthalene-6-sulfonic acid, 2-aminonaphthalene-
5,7-disulfonic acid, 1-amino-8-hydroxynaphthalene-6-sulfonic acid, 1-
amino-8-hydroxynaphthalene-2,4-disulfonic acid, 2-hydroxy-3-aminonaph-:.
thalene-5,7-disulfonic acid,:l-amino-8-hydroxynaphthalene-2,4,6-tri-
sulfonic acid, l-hydroxy-8-acetylaminonaphthalene-3-sulfonic acid,
l-benzoylamino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid,
2-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxy-
naphthalene-7-sulfonic acid, 2-methyl- or 2-ethylamino-5-hydroxynaphtha-
lene~7-sulfonic acid, 2-(~-acetyl-~-methylamino)-5-hydroxynaphthalene-
7-sulfonic acid, 2~acetylamino-S-hydroxynaphthalene-7-sulfonic acid,
2-amino-5-hydroxynaphthalene-1,7-disulfonic acid, 2-amino-8-hydroxy-
naphthalene-6-sul~onic acid, 2-methyl- or -ethylamino-8-hydroxynaphtha-
lene-6-sulfonic acid, 2-(N-acetyl-~-methylamino)-8~hydroxynaphthalene-
6-sulfonic acid, 2-acetylamino-8-hydroxynaphthalene-6-sul~onic acid,
2-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2-acetylamino-8-hy-
droxynaphthalene-3,6-disulfonic acid, l-amino 5-hydroxynaphthalene-7-
sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic
acid, l-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid,
1-(4'-aminobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-disulfonic
acid, 1-(4'-nitrobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-di-
sulfonic acid, 1-(3'-aminobenzoylamino)-8-hydroxynaphthalene-3,6- or
-4,6-disulfonic acid, 1-(3'-nitrobenzoylamino)-8-hydroxynaphthalenè-
3,6- or -4,6-disulfonic acid, 2-(4'-amino-3'-sulfophenylamino)-5-
hydroxynaphthalene-7-sulfonic acid, 3-methylpyrazolone-(S), l-phenyl- -
3-methyl-5-pyrazolone, 1-(4'-sulfophenyl)-3-methyl-5-pyrazolone, 1-(4'-
sulfophenyl)-pyrazolone-(5)-3-carboxylic acid, 1-(3' aminophenyl)-3-
methyl-5-pyrazolone, 1-(2',5'-disulfophanyl)-3-methyl-5-pyrazolone,
1-(2'-methyl-4'-sulfophenyl)-5-pyrazolone-3-carboxylic acid, 1-(4'~8'-
disulfonaphthyl-[2']-3-methyl-5-pyrazolone, 1-(',7'-disulfonaphthyl-
E 2']-3-methyl-5-pyrazolone, 1-(2',5'dichloro-4'-sulfophenyl)-3-methyl-
5-pyrazolone, 3-aminocarbonyl 4-methyl-6-hydroxypyridone-2, l-ethyl-
3-cynao- or -3-chloro-4-methyl-t-hydroxypyridone-2,1-ethyl-3-sulfo-
methyl-4-methyl-6-hydroxypyridone-2, 2,4,6-triamino-3-cyanopyridine,
- Z3 -
2-(3'-sulophenylamino~-4,6-diamino-3-cyanop~ridine, 2-(2'-hydroxyethyl-
amino-3-cyano-4-methyl-6-aminopyridine, 2,6-bis-(2'-hydroxyethylamino)-
3-cyano-4-methylpyridn, 1-ethyl-3-carbamoyl--4-methyl-6-hydroxypyridone~
(2), 1-ethyl-3-sulfomethyl-4-methyl-5-carbamoyl-6-hydroxypridone-(2),
N-acetoacetylaminobenzene, l-(N-acetoacetylamino)-2-methoxybenzene-5-
sulfonic acid, 4-hydroxyquinolone-(2), 1-amino-8-hydroxy-7-(phenylazo)-
naphthalene-3,6-disulfonic acid, 1-amino-8-hydroxy-7-(4'-sulfophenyl-
azo)-naphthalene-3,6-disulfonic acid, 1-amino-8-hydroxy-7-(2'5'-disul-
ophenylazo)-naphthalene-3,6-disulfonic acid.
Amines of the formula (6)
.. . .. .
l-aminobenzene-2-, -3- or -4-~-sulfatoethylsulfone,
l-aminobenzene-3-~-phosphatoethylsulfone, 1-amino-4-methylbenzene-3-
~-sulfatoethylsulfone, l-aminobenzene-3-~-chloroethylsulfone, l-amino-
4-methoxybenzene-3-~-sulfatoethylsulfone,
l-aminobenzene-4-~-sulfatoethylsulfone-2-sulfonic acid,
l-aminobenzene-5-~-sulfatoethylsuflone-2-sulfonic acid,
l-aminobenzene-5-~-sulfatoethyl-sulfone-2,4-disu~fonic acid9
l-aminonaphthalene-4~-suIfatoethylsulfone,
l-amino-2,5-dimethoxybenzene-4-~-sulfatoethylsulfone3
l-aminobenzene-4-~-sulfatoethylsulfone-2-carobxylic acid,
l-aminobenzene-5-~-sulfatoethylsulfone-2-carboxylic acid,
l-amino-2-methoxybenzene-4-~-sulfatoethylsulfone,
l-amino-2-chlorobenzene-4-~-sulfatoethylsulfone,
l-amino-2-methoxybenzene-5-~-sulfatoethylsulfone,
2-aminonaphthalene-8-~-sulfatoethylsulfone,
2-aminonaphthalene-8-~-sulfatoethylsulfone,6-sulfonic acid,
l-amino-2,5-dimethoxybenzene-4-vinylsulfone7
l-amino-2-methoxy-5-methylbenzene-4-~-sulfatoethylsulfone,
l-amino-2,5-diethoxybenzene-4-~-sulfatoethylsulfone,
l-amino-2-bromobenzene-4-~-sulfatoethylsulfone,
l-amino-2-bromobenzene-4 vinylsulfone,
l-aminobenzene-5-vinylsulfone-2,4-disulfonic acid,
l-aminobenzene-5-~-phosphatoeathylsulfone-2,4-disulfonic acid,
- 24 -
1-2minobenzene-5-~-ch~oroethylsulfone-2,4-disulfonic acid,
2-aminonaphthalene-8-~-phosphatoethylsulfone-6-sulfonic acid,
2-aminonaphthalene-8-vinylsulfone-6-sulfonic acid,
l-amino-2-methoxy-5-methylbenzene-4-~-chlorethylsulfone~
2-aminophenol-4-~-sulfatoethylsulfone,
l~aminobenzene-3- or -4-vinylsulfone,
l-amino-2-hydroxybenzene-4-~-sulfatoethylsulfone,
l-aminobenzene-S-vinylsulfone-2sulfonic acid,
3-(N-methyl-~-sulfatoethylsulfonylamino)-l-aminobenzene,
3-(N-ethyl-~ sulfatoethylsulfonylamino)-l-aminobenzene,
3 ~-sulfatoethylsulfonylamino-l-aminobenzene.
In the manufacture o~ the preferred reactive dyes of the
formula (1), wherein D is the radical of an azo dye which contains
sulfo groups, in particular of a mono- or disazo dye, the diazotisa-
tion of the intermediates which contain a diazotisable amino group is
usually effected by treatment with nitrous acid in an aqueo~s solution
of a mineral acid at low te~perature, and the coupling is carried out
at weakly acid or neutral to weakly alkaline pH values.
The condensation reactions of the 2,~,6-trifluoro-s triazine
of the formula (4) with the organic dyes of the for~ula (5) which
contain sulfo groups, or with the primary products thereof which
contain a -N(Rl)H group, and the amines of the formula ~6),are pre-
ferably carried out in aqueous solution or suspension, at low tempera-
ture ancl at weakly acid or neutral to weakly alkaline p~ value, and
such that a fluorine atom remains as remova61e radical in the end of
the formula (1). The hydrogen fluoride which is liberated during the
condensation is advantageously neutralisedcontinously by the addition
of aqueous alkali hydroxides, carbonates or bicarbonates.
If the reactive dyes of the formula (1), wherein D is the
radical of an azo dye which contains sulfo groups~ contains complex
forming groups in the o,o'-position to the azo group, e.g. hydroxyl or
- 25 -
carboxyl groups, it is also possible to obtain metal complexes of the
a~o dyes of the formula (1) by treating the azo compounds which contain
complex forming groups in the o,o'-position t~ the a~o g~oup, before,
or optionally also after, the condensation with the 2,4,6-trifluoro-s-
triaæine of the formula (4), with metal donors.
Copper complexes of azo dyes of the formula (1) are of parti-
cular interest. A suitable method of metallation, in addition to that
described above, is also that of dealkylati~g metallation and, for the
production of copper complexes, oxidative coppering.
The dyes of the formula tl) are fibre-reactive, as they con-
tain a removablP fluorine atom in the s-triazine radical.
By fibre-reactive compounds are meant those compounds which
react with the hydroxyl groups of cellulose or with the amino groups
of natural or synthetic polyamides to form ~ovalent cbemical bonds.
The dyes of the formula (1) are new. They are distinguished
by high reactivity and produce dyeings having go~d wet- and lightfast-
ness properties. They have in addition good fixation properties and
produce dyeings of notably high tinctorial strength. The good build-up
of the red azo dyes of the formula (1), in particular of those of the
formula (2), on bleached cotton yarn, is to be singled out for special
mention.
The reactive dyes of the formula (1) are suitable for dyeing
and printing a very wide variety of materials, snch as silk9 leather,
wool, polyamide fibres and polyurethanes, but especially cellulosic
materials of Eibrous structure, such as linen, cellulose, regenerated
cellulose, and especially cotton. They are suitable both for dyeing by
the exhaust method and for dyeing by the pad-dyeing process, in which
the goods are impregnated with aqueous and9 if desired, also with salt
containing dye solutions, and the dyes are fixed after treatment with
alkali or in the presence of alkali, with or without the application
- 26 -
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.
The manufacture of the mono- or disazo intermediates is not
described in ev~ry case in the Examples, but it can be readily inferred
from the foregoing description.
In the following Examples, the parts and percentages are by
weight.
- 27 -
Exa~ple 1: 24.5 parts of the dye of the formula
03SCH2 ~ ~ - N ~ 1
L o OH ~H2 _¦ 2 Na (3
2 5
_ . .
are dissolved neutral in 400 parts of water. The solution is cooled
with ice to 0-5C and then, at this temperature, 7.1 parts of 2,4,6-
trifluoro-1,3,5-triazine are added dropwise in the course of 15 min-
utes, whilst keeping the reaction mixture at pH 5-6 with the simultane-
ous addition of sodium hydroxide solution. As soon as no more starting
dye can be detected by chromatographyJ 14.8 parts of 1-aminobenzene 3-
~-sulfatoethylsulfone are added. A pH of 6 to 6.5 is maintained by
continuously neutralising the liberated hydrogen fluoride with
2N sodium h~droxide solution and raising the ~emperature to 20C.
When the reaction is complete, the reactive dye is salted QUt with
sodium chloride, collectad by filtration, washed and dried in vacuo.
It is a yellow powder and dyes cotton and regenerated cellulose in
clear yellow shades.
Dyes with similar properties are-obtained by condensing the amino
dyes of column 2 in Table 1 with equlvalent parts of 2,4,6-trifluoro-
1,3,5-triazine and immediately thereafter with the amines of column 3
in accordance with the particulars of this Example.
-- 28 --
__ ._ _
CO ~I ~ ~ ~ ~ ~ ,_ o
_ _ _ ID
I I I I I I I ~ i I I ~-
p r~ P ~ ~ P Y ~
C O 'C O 'd O ~ O ~ O ~ O O O C O ~ O
t P ~-- ~ Y ~ P 1-- P X P ~ P
P~ P p~ J p.) (D P~
~t p ~' p 5 ~ ~' ~ p~ r p. ~
~ 0 5 0 ~ J :~ O ~r r ~5' 0 :J
p N P N P P P N P~3 P::1 N ::1
~D p ~ ~ ~ p ~D p~
Jl O1-- t--ID Y
`' CO ~ ~
CL~ N P~ ~ ~ t '~
Y~ ~' P
O
~:: C ~:: 5 ~ C ~ C C P.
~q
~ p ~0 pO p p ~ p pO ~D
n n n n n n n n n
n n n n n n n n n
l l l l l l l l l
a ~ a ~ ~ ~ a 1
P P P P P P P ~ P
' 0l 0l 0l 0l 0l 0l 0l 0l
_ _
~ I C I ~ I ~ I ~ I
t~ Yp~ O
a
. ~ p. ~ . p, .
O O O O O O P~ O O O ~-
C ~ O
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O O O ~ N ~ N ~ Nrl N . ~ N
. . . ~ ~ )
ta ~ p ~
C ~ C ~ C ~ ._
I~ h
O I O I O I~' I O
P ~:a P ~ ~ ~ P
I (D (D I p I ~ I
_ _ _ _
~ P.
0 1- ~ O 1- 0 0 0 0 ~ ~ P
~ . ' O 1' On
P
_ _ ,
- 29 -
<IMG>
-- 30 --
~ _ ~
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I I ~ II 'q I I ~ I ~I I I I I ~ I I
~ ~ P~t ~I) pt~ tD P~S ~D ~P P t~ p ~1 ~ p~
p ~ 31~ ~ 3 ~ rr 31~ 3 5E3E~ E3 r~
O `- p' o ~ p' 0~ ~,<5 p' o~ ,~ ~,, p' ~ ~ p~ ~ . . P
~ ~nO p !--o ~ o ~ Po o o o o P o o rr
o _ I t~) II rD I I ID I 3~ P P I P 1-- ~ ~ 1.-.
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~ . p 1~ I p ~ I p ~ I o s CJ' ~ ~ '1 ) p~
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n ~^ . ,~
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~n ~P ~ 3 p ~D ~ _~
p,1 3 o ~t 3 l t rt 3
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N ~_ ~ N ~ 3 NCl. 3 1~ h I O
o ~ o ::1 o rt
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p a~ 5 a~ p Y a~ ~-- a O C
'q I~C I ~ I I I p p p ~ ~_
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p p 1 ~
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rt nIt n ~, X n X P n ~-- n
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- 43 -
Example 2: 22 parts of 2,4-difluoro-6-(4'-~-sulfatoethylsulfonyl-
phenylamino)-s-triazine are added at 20C to a neutral solution in
500 parts of water of 30.5 parts of the trisodium salt of the amino-
azo dye obtained by coupling diazotised 2-aminonaphthalene-3,6,8-tri-
sulfonic acid with 3-aminophenylurea in acetic acid medium, whilst
keeping a pH value of 6 to 6.5 by the constant addition of 2N sodium
hydroxide solution. The condensation is continued until no more
starting dye can be detected by chromatography. The dye of the formula
.~ \./ ~./ N \ / NH ~ ~ - N~--\ /--S02CH2CH20S03H
H0 S/ ~-/ \-~ \S0 H 2
is:salted out with sodium chloride, collected with suction, washed
and dried. It dyes cellulose materials in very fast reddish yellow
shades.
Table 2 lists further dyes which are obtained in analogous manner
by reaction of the amino dyes in column 2 with the primary condenbat~
ion products of 2,4,6-trifluoro-1,3,5~triazine and amine in column 3.
.. . , . . . ... . . , . ... , .. ~ . ,.. .... . ~ .. .. ., , ... . . ~ .. .. ............ ..... .............. . ...... . . . . . .
.. .. . . .. .... .
-
-- 44 --
~ ...... ... . ~
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-- 45 --
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h
O O O O O 0
P ~ ~ ~ P
I ~ 1 1 ~'
'~ I I ~
___ _ ___
~ 5
'. ~ ~
~' ~0 Po' ~ ~ f~)
tD ~ C ~D ~ ~
n o
:L
-- 47 --
, _, _ __ _ _ o
~ ~ ~ ~ V'
_ _ _ ~
~ n I Ga N n I ~D p n n I u~ P~ C I
C 1~ (1) I N 1~ ~ ~ 5 Hl ~
~ p ~I P p ~ p~ po ~ p ~ o n
O O O ~ ~ O ~ ~ ~D O ~ Y~ O P~ O
P ~ I ~h ~ I1-- C I ~ n X ~: P
1~ 5 ~ ~ 5
n n I rD rt I ~ ~,
~ 5 P~o~ Op 3 ~ I n I C~
n ~ P~
-- n P~ 5 ~ ~ 3 rr
N ~ ~C P E~ , ~ I I , ~ :~1 P
Q CO :3 0~ ~ N ~ 1'1 1 1 . .
,~ l 3 o ~
D n ~ n
~ ~ p o~ ~ ~ o I ~ I
P~ N C ~1 N ~ ~ g(~) lo-h 0
ID ~ p ~ P tDP. ~ ~tl p CO P~
p ~ ~ I n ~
I ~ a~ ~ p
ul ~ ~n C ~ !~ C P~ C~ C;~
;:~ 0 3 N
O C~~:J O rr `'I P I ~D
n' 'd ~ I n' ~
I n ~ I .
_ _ __ _ _ 1
. o~ c~
I C I I O
p ~ ' P~ :1
CJ' n C p P
n :~ ~ P ~ ~.
Ul N n N :~ O
~ ' P 5 ~5
3'D.' (D~ (~1 Il)
~ I I I o
P P~ P It ~
J-
O O
~, C ~ ~ O
~ Y~
O I I 1: N
P P~
~ .~ ~ ~
C C C n
r~
." ~ O
- 48 -
,.
Example 3: 16 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic
acid are dissolved neutral in 400 parts of water. The reaction solution
is adjusted to pH 4.5 and, with good stirring, 7 parts of 2,4,6-tri-
fluoro-1,3,5-triazine are added dropwise at 0 to 3C. The liberated
hydrogen fluoride is neutralised by the metered addition of 2N sodi-
um hydroxide solution. As soon as no more free l-amino-8-hydroxy-
naphthalene-3,6-disulfonic acid can be detected, 10.6 parts of
l-aminobenzene-3-~-sulfatoethylsulfone in 50 parts of water are ad-
ded. The ~emperature is allowed to rise to 20-25QC and the pH of
the reaction solution is kept at 4 to 4.5. When the condensati~n is
complete, the dyestuff intermediate is coupled at 0 to 10C with 15
parts of diazotised 2-aminonaphthalene-1,5-disulfonic acid. At a
final pH of 6.5 to 7, the dye of the formula
. ~ 3H H~ ~H ~ - NH~
i, I t il i ~ \s02CH2CH20So3H
H03S ~ S03H
03H
is salted out with sodium chloride, collected by filtration, washed
and dried in vacuo. It is a dark red powder and dyes cotton and
regenerated cellulose in bluish red shades of good wetfastness and
good fastness to rubbing and light.
Diazo components whose coupling energy is sufficient for coupling
in a pH range from 4 to 5.5 can be coupled to the primary condensation
product obtained from coupling component and 2,4,6-trifluoro-1,3,5-
triazine. The reaction with the amine then follows in the final
step.
Table 3 lists further dyes which are obtained by reaction of
2,4,6-trifluoro-1,3,5-triazine with the coupling components of column
2, then with the amines of column 3, and finally by coupling with the
diazo components of column 4.-
- 49 -
_ , - , _
CO ~I ~ ~ ~ W ~ ~_ Z ~3
I~ I g ~D
~D O tD 0~ ~ O ~ O ~ P P w
O O O 1~ J~ 5 1~- 5 n
~ El
~ rt
n ~ ~-h `< p ~ p~q~ X P
P' ~ n' I n ~ ~ P' ~
_ ~ - .. 1-- 1 . I_ _
~ n P~ a ~ a
~ ~ ~ p ~ ~ C ~ ~D p C O
oh g ~ ~ Ho~ oh ~ oh p o P !~
~ p N C 5 P N P N ~ 5 P N ~ N 1~-
O 11~ D p(D p U~ 5 p g P
~ P 1' 1 ~
C
. C 1 0I p,
. .~
o I n I I I n I cI I tf
, O ~ ~
3- r~ P ~P I N ~p3
~ rP~
~ ~ N P 1--
`' I C C ~D P :~
n i I n
C pO n n ~ n
I . n n P
c~ ~ n
. - ~ ~
o o o o o o o ~ ~
- 5~
26.8 parts of 1,4-diamino-2,5-dlsulfonic acid are dissolved
neutral in 250 parts of water with the addi~ion of sodium hydroxide.
After addition of 2,8 g of disodium phosphate, 13.6 parts of 2,4,6-tri-
fluoro-1,3,5-triazine are added dropwise at 0C in the course of 5
minutes while keeping the pH of the reaction mixture at 6 with 2N
sodium hydroxide solutiou. When the condensation is completP, a
solution of 28 parts of 1-aminobenzene-3~-sulfatoethylsulfone in
100 parts of water is added and the pH is kept at 6.5 by the simul-
taneous dropwise addition of 2~ sodium hydroxide solution. The tem-
perature is allowed to rise gradually to 20C. Then 7 parts of solid
sodium nitrite are added and, after this has dissolved completely,
the reaction mixture is poured onto a mixture of 25 parts by volume
of 10~ hydrochloric acid and 100 parts of crushed ice. A neutralised
solution of l-ethyl-3-sulfomethyl-4-methyl~6-hydroxypyridone-(2)-
5-carboxamide in 100 parts of water is then poured into the diazo
solution. The pH is adjusted to 6.5 and the reaction mixture is stir-
red at this pH value until the coupling is comple~e. The dye of the
formula
OH ~ N ~
C2H5 S02CH2CH2 S 3-
is precipitated with sodium chloride and then isolated, dried and
ground, affording an orange powder which dyes cotton from an aqueous
bath in strong, slightly reddish yellow shades.
Table 4 lists further valuable dyes which dye cellulose in the
indicated shades and which are obtained by using the amines of column
2 instead of l-aminoben7ene-3-~-sulfatoethylsulfone and the coupling
components of column 3 instead of 1-ethyl-3-sulfomethyl-4-methyl-6-
hydroxypyridone-(2)-5-carboxamide after the condensation of 2,4,6-
. .
34
- 51 -
trifluoro-1,3,5-triazine with 1,4~diaminobenzene-2,5-disulfonic acid.
Dyes with similar properties, but which produce more hy~sochromic
shades on cellulose material, are obtained by using 1,3-diaminobenz-
ene-4,6-disulfonic acid instead of 1,4-diamino-2,5-disulfonic acid.
,
:, ' : . '
3~
-- 52 --
_ _ . _ ,
Z P~
. ,. __. . ___ _ . .. _. _ . _ _ . ~
t , 3, ~ , , rD
3, ~ ,3. o~ 3
N N 3 I N 3 ~ N N ~ N
P P' I ~ P
~ I Cpr ~ ~1 p ~ I O O I ~1 0 1 P
~ ~N p~ ;) N l-h ~ ~ ~ .
~ D 0,~ C ~ C
~ 3 ~ ~ ~
O O O ~- fD C ~0 0
~ 5 h ~ ;. O
C C ~~ ~ ~ C ~ ~
o o I o l-h ~h
~ ~ pO , P 0~ ~0
__. _ . . .. _ _ ... ___ _____ _
0
~ ~ o~ o o o 8 ~ ,_ Y co ~ ~n c ~
3 ~ o - ~ ~
, tutotU rc~ ~ ~ 3 ^ t I_
O ~ J ~ ~ t ~ o ~ n C ~ D
3' ~ ~ Co ~ O ~ t ~ 1 0 ~ aq
I tu P t tU t I ta 1 I g
(D ~ U l-h ~It P '~ i I El
n 0 3 1 1 1 ~ ~ s N 3 ~
'~h C ~::1 ~ ~ ~ 5 ~ ..
~D Y h~ o ~, ~ ~ ~3 P
P tl~ :I tD Y I ~¦ ~ o
n~ tD I Y
t~ t L
O O' ~~
. - .. _ .
C t~ ~ ::~
~ . ~ ~ ~
& n t~ t~ tl~ 5 ~ ~ ~0
~D ,0~ O
_I_ rr
, . ~ .. ___. - . - ~---
-- 53 --
; ' 1~ O' V`
~ 10
- P P P .
cl 5 ~ ~ P
tO (~ P~ r
P p ~ ~_~
W O W r~ O ~ P- C
~ tD :~
C ~ I .. : .
P~ P' 5
O ,_
tD
~ ~ o~
o~
It~
pO ~h ,1
(D P
g~ E., P-,
E ~ ~ n c p,
W ~ ~
,1 o ~ ~ ~ 5 o
cn , ~ o 11 ~ o o
W~
; I ~ W .,
~ I'' ''' C
~ ICJ ~
t pO
c ~ c-. n
. ~
., ~ .
. .
3~
~!-
.
P'
~P' ,
~ T
. ~ ~o ~o
= ~
.
q33~
Example 5: 51.5 parts of aminophenylnaphthotriazole o the formula
SO3H
/ ` ~\ N~32
H2N 3H
are dissolved in 90O parts of water at pH 5. Then 13.6 parts of2,4,6-trifluoro-1,3,5-triazine are added dropwise at 0C and the pH
is kept constant with 2N sodium hydroxide solution. When the reaction
is complete, a solution of 7 parts of sodium nitrite in 50 parts of
watèr is added to the reaction mixture,-which is poured onto 25 parts
by volume of 10N hydrochloric acid and 100 parts of crushed ice. Any
excess nitrous acid is destroyed after an hour with amidosulfonic acid.
To the diazo suspension are added 25.4 parts of 1-(4'-sulfophenyl)-3-
me~hylpyrazolone ~5) and the pH is kept cons~ant at 5 with 2N sodium
hydroxide solution. When the coupling is complete, 28 parts of 1-
aminobenzene-3-~-sulfatoethylsulfone in 100 parts of water are added.
The pH is raised to 6.5 and the temperature is allowed to rise ~radually
.. ...
to 20C, When the reaction is complete, the dye of the formula
OH HO3S
3 ~ ~ ~ ~N~y,~r~ S03H
W~
NH ~
5 2C 2 2 3
is salted out and isolated by filtration and dried. It is a
yellowish orange powder which dissolves in water to give a yellow
solution and dyes cotton in yellow shades.
The dyes listed in Table 5 are obtained in analogous manner -
by diazotising the compounds of column 2 after treatment with the
reac~ive component, reacting further with a coupling component of
column 3 and finally condensing with the amine of column 4.
.. . . . - -- - :
3g~
_ .. . . ~_ ....
Cl~ Z P~
.... _ ~ _ ~D
O O O O O ~ a,
. ~ ~ P
~U~ ..
3~
~ ;
~ . .
3 ~ c
~: C ~ C) O ~`
P' ~ I o I ~o o
O p~ O fD n P~ ~ _ ~ ~ ~ :1
I-- O N ¦ ~ N 1` ~ O .
~n P ~ rt
~_ ~11 o N I ~.n O I ~ ~
~ _~ 5 ~ C Z ~ ~5
I I . . .! ... - -- . .. _
o o 8 ~ i:
Z ~
O s
~5 (D
I ~~~
_ .. ___ e~~ . ~ . __
Z ~ Z z ~ Z n S
~ _ ~
. . . _ .
34
-- 57 --
'~ o ~ ~ P~
... ~ ~ ._
n ~ I N 5~ N 11
~ . ~ ~cn n o
~ 1 o oo o o ~ ~ ~
. I-h3 Ih O-
P 'd~ O . P
. _.. ,, _ , ,, _. _._.. . ....
3 ~ W ~ O
N -- ~:r ~Q. ~- ~'- _ ~ _ ~r - 1--
O C ~ J C 'C ~ P
P ~ ~ I ~ ~ n
~ ~ @~ ~ p, PN~ ~ ~ N O ~ ~ 3
5 rt ~ O n o 5 1-- p N I rp
a ~ n P~ ~` (D p p o po
I~ O l_ I P C ~
E~ p P ~ 5
~ I ~ p~
~ L . ._ _ .
W I ~: I C I ~ .
~ O O O O 1: ~D
, . ~ 1 .
C C C
O o O
~ 3
- __~
O :~
~ 0~ ~ ~
, .i ~ _
,
.
-- 58 --
..... ._ _ ~ ~3
~ . ~n ~ O
_ _.__ _ ~
. N ( n
C
P
.. . --` _.
P~ ~ I P P ~ g
~ ~ C:
P~ o ~ ~:S
,~ ~ I Iq
,: ': ~ ~ p'~ ~
~ O O l~h O
~ ~ ~, I (D I iD P
O~ ~ U~ ~ ~ ~
~ lot p~ I
~ ~X ~ _
~ .
C~
.. O O O
tD S'S 'd
O ~
P~ ~ ~
~ P~
. . O ~ ~ _
.~ . : ~
:~
_
- ~9 ~
E~ample 6: 28.1 parts of 1-aminobenzene-4-~-sulfatoethylsul~one are
dissolved in 200 par-ts of water at pH 5. Then 13.6 parts of 2,4,6-
trifluoro-1,3,5-triazine are added dropwise at 0C in the course
of 5 minutes while adding 2N sodium hydroxide solution to ensure
that the pH does not rise above 6. When the condensation is complete,
a solution of 21 parts of the sodium salt of 1,3~diaminobenzene-4-
sulfonic acid is added to the solution of the monocondensate.
Condensation is carried out at pH 5 until no more diamine can be
detected, and the temperature is allowed to rise to 20C. The con-
densation product, which still contains a diazotisable amino group,
is then diazotised in accordance with the particulars of Example 4.
To the solution of the diazo compound are added 40.5 pa~ts of the
disodium salt of l-acetylamino~8~ hydroxynaphthalene-3,6-disulfonic
acid and coupling is subsequently carried out at pH 6 to 6.5. The dye
of the formula
H03S
C~3 ~ N = ~ ~ ~ F
H03S S03H NH ~ S02CH2CH20503H
is precipitated with potassium chloride, isolated and dried. It is
a red powder which dyes cotton in brilliant red shades.
Table 6 lists further dyes of this invention which can be
obtained by condensing, according to the procedure of this Example,
2,4,6~trifluoro 1,3,5-triazine firstly with an amine of column 2 and
then with adiaminobenzenesulfonic acid of column 3. Diazotisation of
the secondary condensation product and coupling of the diazo com-
pound to the coupling component of column 4 yields reactive dyes
which dye cotton in the light- and wetfast shades indicated in column
5.
. ~
~ 60 --
_ _ _ . ___ _ _ , _ ~3
I~ O ~o co ~I a~ ~n ~ . ~ ~ ~_ O P~
. _ ............. . ~_
C, C
~' cr~
P~ . ~D
r~ P ~ ~
~~ o o ~ ~ ~ ~ o o
o o o ~ p o o o o oo
' ~ W ' ' ' ~ W
~ ~D Y ~
C ~, ~ P~
~h ~ ~h ~
. ~ I ~ol .
.
. .. ,__
~ ~ ~ 1-- U~ t~
C ~ C ~ C l'
oh I ~ , oh i,~
O tl~ ~, P P
. ~ n ~ ' ~J
O O O ~ O O O O O O 1'~
~, ~o ~ ~o P' W
(D . P~ ~D ~ P
N N
o P :
_ I I
, . ,- _
Y~ 1 5 1 I C 1 1 1 ~ I ~: 1 11) 1 1 1 O
C tD ~h Pn~ n 5 ~ w w
1-- 0 0 ID !:L~ O,3 1'~ 1' N ~ 1--
ttl N p l't It p~D O O O ~ O ~ I I
' ~ ;~ n' ~ ~ P n I lo - ~ - C C P
n p, ~ ~ ~ p, ~ P' ~ I I ~ I ~C I ~ ~h n
3 n ~ ~ n Ps 3- 3~ ~ tO I Y- ~ ~- o o O
' ~' O :1' ~' g ~ ~, I C ~n C O S ~ ~ O
I ~n ~ O 1~ Y I O ~h O O O ~ P
0~ D n n 3 o p r~ ~C ~ n
(D p 0~ r~
P ~ I I C ::~
~ -
o ~
,~ ~ C 3 1~: c ~ ~D
p p~ h ~ 3 ~ ~ .
p~ ~ ~ p rw O ~D n ~ O ~ '<:
~ E` ~ ~ ~, ,
C ~ ~ ~ D
~ p, ,_.~ o ~ l ~ '
p ,_ ~ ~ p D~ I ~ ~ P'
~ O~, ~ n I ~ '~ 3~ PN~
P (I~ b 5'(D I O O
' n P ~ ~ o t
_1 ~D n ~:J I ~
n' I ~ . rOS ~: ~d p~
X I P~ I
I ~ ~ O ~JI
_ _ . ~;, . _
r~ O U~ O O ~ n co
n It n rs It ~D o
O 0~ g 0~ 0 oP' 0~ 1- rt
~ ~o ~o
' . P
.
. , ~ . _
.
0;3
-- 61 --
L ~ o ~3
.
,.. C~
s~ ~ ~ o
o o o e
P
_ _
C ~ C~-
P ~ ~ ~
oP~ ~ n t
. p, p . P~ P
n o ~ N
Y` V' 1-` ~D
P. p ~ P
Pl
O ~ ~ t ~ C
or~ F~ ~ c n ~
N ~- ~ I_~
5 0~ ~ p 'q P
~ Y~ p~
_, o I ~ n
~ ~t~ I O
C C ~ r~
~h ~h 11
~ 3
~D ~D I
~ ~ ~ .
, ~, ~
F~ i ~
,.. , ......... __
.,
~ O
(D ,_ ~ ~r P'
~1
- 62 -
Dyeing Procedure 1
2 parts of the dye obtained according to Example 1 are
dissolved in 100 parts of water while adding 0.5 part of sodium
n-nitrobenzenesulfonate. A cotton fabric is impregnated with the
resulting solution to a liquor pick-up of 75% and then dried.
The fabric is then impregnated with a warm solution of 20C
whi~h contains9 per litre9 5 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 ~o 101C, rinsed, soaped for a quarter
of an hour in a 0,3% boiling solution of a non-ionic detergent,
rinsed and dried.
Dyeing Procedure 2
2 parts of the dye obtained according to Example 1 are
dissolved in 100 parts of water. The solution is added to 1900 parts
of cold water, 60 parts of sodium chloride are added and 100 parts
of a cotton fabric are put into this dyebath. The temperature is
raised to 40C and 40 parts of calcined sodium carbonate and another
60~parts of sodium chloride are added after 30 minutes. The tempera-
ture is kept for 30 minutes at 40C. The-dyeing is rinsed and then
soaped for 15 minutes in a 0.3% boiling solution o' a non-ionic
detergent, rinsed and dried.
.
