Note: Descriptions are shown in the official language in which they were submitted.
-
~ 3 ~
Description
~ater-~oluble azo cGmpound~t preparation and use thereof
~ dyes
S The present inv~ntion relates to fiber-reactive dye~.
The present invention provides novel, u~eful fi~er-
reactive monoazo compound~ which po~e~s fiber-reactive
dye propertieg and conform to the general formula (1)
OH
X N - D -N ~ N ~
R ~ (1)
COOM
where the variables have the fDllowing ~eanin~:
D i~ a para- or meta-phenylene group which can be
~ubstitut0d by 1 carboxy group or 1 to 2 sulfo
group6, or i~ ~ naphthylene group which contains the
azo group bonded in the 1- or 2-position and to
which the grouping X-~(R)- i8 bonded in the 5- or 6-
po~ition and which can be substituted by one car-
boxy group or 1 or 2 ~ulfo group~,
R i8 a hydrogen ~tom or an alkyl group of 1 to 4
carbon atoms, such a~ methyl or ethyl, or i~ a
hydroxy-, cyano-, carboxy-, sulfo-, sulfato- or
phosphato- or phenyl- or ~ulfophenyl-~ubstituted
alkyl group of 1 to 4 carbon atoms, ~u~h a8, for
example, a benzyl, phenethyl, ~-cyanosthyl ~-
carboxyethyl; A-sul~oethyl~ B-~ulf2toethyl/ ~-
phosphatoethyl or ~ulfomethyl group, of which
preferably hydro~en or me~hyl~
i~ a hydro~en atom or an alkali metal or one
~guivalent of a dival~nt ~etal, a of an alkaline
earth metal, a~ for example of calcium, but prefer-
ably hydrogen or an alkali m~talt such a~ ~odium or
i
.
~, , .
- 2 - ~32~
pc~ta~si~m or l ithi~m,
a group of th0 general formula ~ 2 )
Rl N~N
R2~NJ~N~ (~)
where
Y is halogen, ~uch a~ fluorine and in particular
ehlorine,
Rl i~ a hydrogen ~tom or an alkyl group Df 1 to 4
earbon atom6, 6uch as ethyl or methyl, or i6 an
allsyl group of 1 to 4 carbon atoms which i8 8ub-
~tituted by a sulfo, earbo~y, pho~phato, sulfato,
hydroxy or eyano ~roup and/or by a phenyl or naph-
thyl radieal whieh may lbe substituted by 8ulfo,
c:arboxy ,, alkyl of 1 to 4 earbon atoms, alkoxy of
to 4 carbon atoms, ehlorine and/or nitro and
R2 is ~ hydroslen ~tom or ~n allcyl group of 1 to 4
earbon atom6, ~ueh as ethyl ox ~ethyl, or i~ an
alkyl group c)f 1 to 4 earbo~ atoDIs which i~ ~ub-
st~tuted by sulfo, earboxy, pho~phato, ~ulfato,
hydro~ yano or by a ph~nyl or naphthyl raclieal
which ~ay b~ substituted by ~ulfo, earboxy, ~llyl
of 1 to 4 earbon atoms, alkoxy of 1 to 4 earbon
~tom~, ehlorine ~nd/or nitro, or denotes a phenyl
radieal which ean b~ substituted by 1 " 2 or 3
511b~;t;itUent8 selec~ed from the ~roup consisting of
the following ~ tituent~: 2 alkyls of 1 to 4
~arbon ~toms " ~uch as ~thyl and in particular
methyl, 2 ~lkoxi~ of 1 to 9, carbon atoms, 8UC~ as
ethoxy and ~e~hoxy, 1 bromine, 2 chlorinQs, 3
sulfos, 2 carboxys, 1 nitro, 1 alkylsulfonyl of 1
to 4 caxbon a~om~ which may be ~ tituted by
hydroxy ( such a~, fr: r ea~ample, fl-hydroxyethylsul -
iEonyl ), 1 alkyla~aino of 1 to 4 carbon atoms and
alkylamino of 1 to 4 car~on at~ms which may be
sub~titut~3d ~ n the alkyl radical by hy~oxy,
- 3 ~
~ulfato, ~ulfot phosphato, alkanoyloxy o~ 2 to 5
carbon atoms or by carboxy -substituted alkanoyl-
amido of 1 to 4 carbon ~toms in the alkylene radical
~uch as ~uccinamido, or R2 denotes a monosulfo-,
disulfo~ ox trisulfo-n~phthyl radical,
R1 and R2 being identical o or different from each other,
or
R' and ~2 togekher with the nitrogen atom form a h~tero-
cyclic radical composed of an ~lkylene radical
composed of 3 to 8 carbon atoms, preferably of 4 to
6 carbon atoms, ~r a further heteroatom, such us a
nitrogen atom or oxygen atom, and two alkylene
radical~ of 1 to 4 carbon atoms, ~uch as 9 for
example, a piperidino, pipera2ino ~r morpholino
radical~ .
Substituted alkylamino ~ubstituents in a phenyl ra~ical
R2 are ~or example ~-~ulfo~thyl~mino and B-~uccinamido-
ethylamino.
Of th~ azo compounds of the general formula (1) according
to the invention, e~pecially preferred one~ are tho~e
where R ~tands for hydrogen~ tho6e where D i8 a met~- or
para-phenylene group each substituted by 1 or 2 ~ulfo
groups, those where R1 i8 hydrogen and R2 i~ phenyl which
ifi ~ubfitituted by a sulfo group and ~ay additionally be
6ub~tituted by a further ~ulfo group or a ~ethoxy group.
~ulfo groups are gxoups conforming to the general formula
-SO3M, carboxy group~ are ~roup~ conforming to the
~eneral formula -COOM, ~ul~ato group~ are groups conorm-
ing to the general f~nmul~ -OS03M and phosphato qroup~
are group~ confoxming ~o the general formula ~OPO3M2, in
each of which M ha~ one of the ~bovementioned ~eanings.
~he novel azo compound~ can be present in acid form and
in the form of their 6alt8. Prefexably they are in ~he
form of their salts, in par~icular alkali and slkaline
~arth metal Raltfi, and are preerably al~o used in the
~.
:
~32~
- 4 -
form of the~e ~alt~ for dyeing (to be under~tood here and
hereinafter in the general ~en~e snd a~ including print-
ing~ hydro~y- and/or carboxamido-containing materials,
in particular fiber material~.
The present invention further relateB to proc~se~ for
preparing the compounds of the g~neral formula (1), which
compri~e
a) reacting ~ compound of the ~eneral f~xmula (3)
OH
H N D - N ~ N ~
R ~ (3)
COOM
where R, D and M have the ~bo~mention0d ~eanings,
ln a conventional manner with a c~pound of the
general formula (4)
X - Y (~
where ~ and Y ha~e the abovementioned ~eanings
15 or
b) dia~oti~ng an ~romatic amino ~ompound of the
general formula (5)
X - ~ - D - NH2 ~5)
where ~, R and D have the abovementioned meanings,
and coupling the diazonium salt with 2~naphthol-6-
carboxylic acid ~r a salt of this carboxylic acid,
or
c) reacting a compound of the general formula (6)
~32~
Y--~N~N--D--N = N ~ (6)
~ OOM
where ~he two ~ and also R~ D and M have ~he
abo~rementioned ~eanings, wi~h an ~nino compound of
the general forJnula HNR1R2 with Rl and R2 of the
abovementioned ~eaning.
~he r~action conditi~ns o proce~e~ a ) and c ) ar~
analogou~ to known proce~se~ of reactin~ amino compounds
with dihalotriazinylamirlo compounds, iEor in~tance in an
~queous or aqueous organic medium (where the t)rs~anic
lû ss~lvent component i~ a preferably water-so~ e ~ol~ent
which i~ inert under the reaction condition~, for example
acetone, di~nethylformamide or dimethyl ~ulfoaside), at a
pH bs~ween 1 and 7, in paxticular be~ween 2 and 6, and at
a te~nperature of between - 1 0C and ~80C, in particular
-lODC and ~53C. In the same way, the diazotization and
coupling ri~a~tion of proce~s variant b) is carried out in
c:onventional ~anner/ for instanc~ the diazotization at
a t~mp@rature of ~etween -5~ ~nd ~20C at a pH of 2 or
le~ than 2 and the coupling reaction ~t a tempera~ure of
between 5 find 2SC and at a pH b~tween 4 and 8, prefer-
~bly between 5 and 7, each preferably in an agueous
medium.
The ~tarting compound~ ~f the general ~onmula ~3~ are
easily preparable ~nalogou~ly to known pxoce~e~ by
coupling the dia~otized ~mine ~R~N~D NH2 with D and R of
tbe abovementioned meaning with 2-hydrox~naphthalene-6-
carboxylic acid or a ~alt of this carboxyl~c ~cid in
accordance with the above reaction conditions for diazo-
tization and coupling~ Not ~nly ~he~e diamino compounds
but al~o 2-naphthol 6-carboxylic acid axe generally known
. .
. , - . . -.~ .
; ' ', ' ,~ ! ' ' ' , ' ' ` . , , '
- 6 -- ~32~l.;13
and described in the literature.
Similarly, the starting amino compound~ of the general
formula (5) containing the ~iber-reactive radical ~ or
the dihalotri~zine radical are generally known; they can
be pr~pared by reacting the corresponding di~mino com
pound of the general formula H(R~N-D-NH2 with D ~nd R of
the abovementioned meaning with an aminohalotriaæine
compound conforming to the general formula (4~ or with
cyanuric chloride or cyanuric fluoride. Similarly, the
starting compounds of the general formula (6) are prepar-
able analogously to other azo compound~ which contain a
dihalotriazinylamino radical in bonded form by reacting
an aminoazo compound conforming to the general formula
13) with cyanuric chloride or cyanuric fluoride. Process
conditions for such reactions are generally known and
e~sentLally conform to the process conditions ~pecified
hereinafter for the rea~tions between starting compounds
(3) and (4) or Qtarting c~mpounds ~6) and amino c~mp~und
NHRlR2
To neutralize the hydrogen halide freed in the cour~e of
condensation reactions, u~e i~ ~enerally made of alkali
and alkaline earth me~al carbonates, alkali and alkaline
earth m~tal hydrogencarbonates or alkali or alkaline
earth metal hydrox~des or else alkali metal a~e ates, the
alkali and alkaline earth metals preferably bPing sodium,
potas~ium and calcium; acid-binding agents are al~o
tertiary amines, for e~ample pyridine sr triethylamine or
quinoline.
~ he reaction according to the in~ention between aminoazo
compound~ of ~he general ~ormula (3) and an aminodihalo-
triazine compound of the general formula (4) ~enerally
take~ place, if Y i~ chlorine, 8t a pH between 4 and 7,
preferably ~etween 5 and 6, and at ~ temperature between
0 ~nd 50C, preferably between 10 and 40~C, particularly
prefer~bly between 10 and 30C, and if ~ ifi fluorine, at
a pH between 4 and 7, preferably between ~ and 6~ and at
_ 7 _ ~ ~ 2 ~
a temperature betwean -10C and +40C, preferably between
-10C and ~30C, particularly prefexably between 0C and
+10C.
The reaction according to the in~ention b~twe~n dihalo-
triazinylaminoazo ~smpound~ conforminq to the generalformula (6) and n amino compound of the gen~ral formula
RlR2NH with Rl and R2 of the ~bovem2ntioned mea~ing gener-
ally takes place, if ~ i~ chlorine, at a pH between 4 and
7, prefer~bly between 5 and 6, ~nd at a temperature
between 0 and 50C, pr~ferably between 10 and 40C,
particularly preerably between 10 and 30C, ~nd if ~ is
fluorine, at a pH between 4 and 7, preferably between 5
and 6, and at a temperature between 10C and +40C,
prefersbly between -lO~C and ~30C, particularly prefer-
ably between 0C and +10C.
Amino startin~ compounds conformin~ to the general
formula R1R2NH axe for ex~mple 2-~ulfsaniline, 3-~ulfo-
aniline, 4-sulfoaniline, 2,4-di~ulfoaniline, 2,5-di~ul-
foaniline, 5-~ulfo-2-methoxyaniline, 4-~ulfo-2-methoxy-
aniline~ 5-sulfo-2-methylaniline, 4-~ulfo-2-methylani-
line, 3-~ulfo-4-methoxyaniline, 4-sulfo-2-methoxy-5-
methylaniline/4 ~ulfo-2,5-dLmethoxyaniline,5~ulfo-2,4-
dimethoxyaniline, 4-sulfo 5-methoxy-2-methyl-aniline, 5-
~ulfo-2-chloroanilin~t 3-~ulfo-4-chloro-2-methylaniline,
4-sulfo-5-chloro-2-methoxyanillne, 5- or 6-sulfo-2-amino-
naphthalene, 6,8 disulfo-2-aminonaphthalene, 3,~,8-tri-
~ulfo-Z-aminonaphthalene, 8-sulfo-2-amino-naphthalene,
~,6,8-tri~ulf~-2-aminonaphthalene, 1,5- or 1,6-disulfo-
2-aminonaphthalene, 4,8-di~ulfo-2-amin~naphthalene, 6,7-
di~ulfo-2-aminonaphthalene, 5,7-disulfD-2~amin~naphtha
lene, S- or 6-~ulfo l~aminonaphthalene, 7 ~ulfo-1-amino-
naphthalene, l-~ulfo 2-aminonaphthalene, 3,6 or 4,6- or
4,8-di~ulfo-1-a~inonaphthalene, ~-~ulfoethylsmineJ ~-
hydroxyethyl~m~ne, ~ mekhyl-N-(B-~ulfakoethyl)amine,
~ethylethyl~mine, dimethylamine, diethylaminey fl-carboxy-
e~hylamine, 4-~ulfobenzylamine, 4-sul~phenethylamine,
b4nzylamine, 2-methylaniline, aniline, 4-chloroaniline,
.
~ ':. : - .
~ ."
.~ .. .
: "
- 8 _ ~ 32~
N~ hydroxyethyl)aniline, N-e~hylaniline, N methylani-
line, ~mmonia, morpholine, piperidine and piperazine~
Diamino starting compou~d~ conforming to the ~eneral
formula H(R)N-D-NH2 are ox example 4,6-disulfo-1,3-di-
~mi~oben2ene, 2,5-disulfo-1 4-diaminobenzene, 4 ~ulfo-
1,3-diaminobenzene, 2-~ulfo-1,4-diamino~enzene, 4-ear-
b~xy-1,3-diaminobenzene, 2-carboxy-1,4-diaminobenzene,
2-~ulfo-4-(methylamino)aniline, 4-~ulfo-3 ~methylamino)-
aniline,2-sulfo-4-(ethylamino)aniline,4-~ul~o-3-(ethyl-
aminoJaniline, 4-N-( ~-BUl foethyl~aminoaniline, 4,8-di-
~ulfo-l 7 6-diaminonaphthalene~nd4,8-di~ulfo-2~6-di~mino
naphthalene.
The compounds of the general formula ~1) prepared accor-
ding to the invention can ~e preciplt~ted or isolated
from the synthesis ~olution~ by generally known methods,
for example either by precipitating them from the reac-
tion medium by mean~ of ~lectrolyt~s, for example sodium
chloride or pota~ium chloride, or by evaporating the
reaction solution, for example by ~pray d~ying, in which
c~e a buffer ~ubstance can be added to the reaction
~lutio~.
The azo compound~ of the general formula (1) ~ccording to
the invention - hereinafter referred to as compounds (1~
- have fiber-reacti~e prop~rties and po~ses~ very good
dye propertle6v as alre~dy ~entioned. ~hey can therefore
~e u~ed for dyeing (including prin~ing) hydro~y -contain-
~ng and/or carboxamido-containing material6, in particu-
lar fiber materials. It i8 ~180 possible to use the ~olu-
tiOn obtained in the synthesi~ of the compounds accsr~
ding to the invention, with or without addition of a
buffer xubstance and with or without conce~trating,
directly in dyeing as liquid formulations.
The present inventîon therefore al~o provide~ ~h~ u~e of
compounds (1~ fox ~yeiny (including printing) hydroxy-
and/or carboxamido-containing materials, or proces~e~ for
, :
9 ~ 3 ~ ~
and/or carboxamido-containing materials, or processe~ for
their application to the~e ~ub~trate~. Preferahly the
materials are employed for applica~ion in the form ~f
fiber materials, in particular in the form of textile
fibers, ~uch as y~rns, wound package6 snd fabrics. Thi~
application can be caxried out analogou~ly to known
process~s .
~ydroxy -containing materials are tho~e of a natural or
~ynthetic origin, ~or example cellulose fiber materials
or regenerated product~ thereof, and polyvinyl alcohols.
Cellulo~e fiber materials are preferably cotton but other
vegetable fiber~ a~ well, ~uch a~ linen, hemp, ~u~e ~nd
ramie fiber~; re~enerated cellulo~e fiber6 are for
~xample ~taple and filament vi8c06e .
Carboxamido-contsining materials are for example ~yn-
thetic and natural polyamides and polyurethanes, in
particular in the form of fiber~, for example wool and
other anLmal hair, silk, leather, nylon-6,6, nylon~6,
nylon-ll and nylon-4.
The compounds can be applied to and fixed on the ~ub~
~trate~ ~entioned in accordance with the use accordin~ to
the invention, in particular the fiber material~ men-
tîoned~ by the application techniques known for water-
~vluble dyes, in particular fiber-reactive dye~, for
example by applying a ~ompound (1) in dissolved form to
~he ~ubs~rate or incorporating it therein and fixing it
~hereon or therein with or without heating and/or with or
without the action of an alkalin~ agen~. Such dyeing and
fixing methods are nwmerously de~cribed in th~ patent
literature, ~or example in European Patent ~pplication
publication No. 0,181,585A.
U6ing compounds (1) it i8 p~s~ible not only ~n carbox-
~mido-containing material~, in particular on wool, but
al~o on hydroxy -containing material, in particular
cellulo~e fi~ex ma~exial, ~o produce yellowish to blui~h
:
~2~
-- 10 --
red dyeings and print~ of high color yield and good color
buildup, in which the brillian~ hue i~ retained even in
deep ~hades. The dye~ngs and prints have good fa6tness
propertiPs, such as good light and wet fa6tnecs proper-
5 ties and good pleating fa~tness, hot pres~ fa~tness andcrock fastness.
Of the dyeings and print~ on carboxamîdo-containing
material, in par~icular on wool, the light, wa~h and wet
li~ht fastne~ properties can be singled out, even if an
otherwi6e cu~tomary ammoniacal aftertreatment of the dyed
material $~ dispen~ed with. They are hi~hly compatible
with other fiber-reactiYe wool dye~t which permit~ level
dyeing of the f~er. Similarly, it i~ po~sible to obtain
level dyeing~ on material made ~f wool fibers of dif-
ferent provenience~ with compounds (1), in which case acugto~ary leYeling a~si~tant, for e~ample N-methyltaur-
ine, may be added to Lmprove the leveling properties.
Preferably, compound6 (1) are used for dyeing cellulose
fiber material~. Of the good fa~tne~s properties ob-
tainable thereof, in particular the good wash fa~tnesspropertie~ at 60 to 95C, even in the presence of per-
borates, the acid ulling, cross-dyeing and per~piration
fagtne~s propertie~, the high steam re~i~tance and good
acid, water ~nd seawater fastness propertie~ should be
men~ioned.
The Examples belo~ serve to illustrate the invention.
Parts and percenta~e~ are by weight, unle~s otherwise
8tated. Part~ by weight bear the ~ame relation to p~rt
by volume as the kilogram to the liter.
The compound~ described below in the Exampl88 in terms of
~ormulae are shown ln the form ~f the free ~cid~; in
general, they are prep~red and isolated in the form of
their ~odium or pota 6ium BaltS And are used or dyeing
in ~he form of th~ir 8alts. It is ~imilarly p~sible to
u~e in the synthesis the 5 arting compound& and
:
,
11 ~ 32~
componPnts mentioned in the orm of the free acid in the
examples below, in particular the Table Examples, as 6uch
or in th2 form of their 8alt6, preferably alkali metal
salt~, such as sodium or pota~ium ~al~.
The ab~orption max~ma (~5~ values) given for the visible
region were determined at 20C on the alkali ~etal salts
thereof in aqueous ~olution.
pl~
a) A ~olution of 91 parts of aniline-4-~ulfonic arid in
500 parts of water st pH 6 i~ ~tirred into a
su~pen~ion of lO0 part~ of cyanuric c~loride and 3
parts of a commercially ~vailable wetting agent in
800 part6 of ice and water. Stirring iB continued
for ~ome time at a temperature be~ween 0 and 5C
while the pH i8 maintained between 3.5 and 4.5 by
mean~ of ~odium bicarbonate. ~he ~onversion of the
acylation reaction i~ 99% or higher.
b) The reaction batch prepared under a) is stirred into
a ~olution of 134 part~ of 1,3-diaminobenzene-4,6-
disulfonic acid in about 600 parts of water at a pH
between ~ and 7; the reactivn mixture ~ 8 heated ts
40C, and ~tirring i~ continued at a temperature
between 40 and 45C while the pH i6 ~aintained
between 5 and 6 by mean~ of ~odium bicarbonate,
until the diamino compound is virtually no longer
detectable.
c) ~he batch obtained from the ~econd acylation reac-
tion under b) is admi~ed with 1000 parts of ice and
150 parts by volume of aqueous 31% strength hydro-
chloric acid and diazotized with an aqueous solution
~f 35 parts o~ ~odium nitrik~. The diazotization
mixture obtained i~ added wi~h 8tirrin~ to ~ 801u-
~ion of 94 parts of 2-naphthol-~-carboxylic acid in
about 1100 part~ o wa~er at a pH be~ween 6 and 6.5,
after which the pH i~ ad~usted to about 5 and is
maintained at between 4.5 and 6 by means of sodium
bicarbonate througho~ the entire coupling reaction.
Stirring i~ continued fox ~ome tLmQ until the
, . . . . .
_ 12 - ~32
couplin~ has ended.
~he novel m~noazo compound thus prepared i~ i~olated in
a conventional manner, for example by evaporating or
spray-drying the neutral ~ynthesi~ ~olution or by ~alting
out with sodium chloride or pota6sium chloride. An
~lectrolyte-containing orange powder i~ obtained of thP
~lkali metal salt of the compound of the formula
Cl OH
N ~ N I -
3S ~ H03S N - N ~
OOH
( ~ax ~ 478 nm)
which shows very qood fiber-reactive dye propertie~ and
applied to the material6 ~entioned in the de6cription, in
particular cellulo~e-fiber material~, for ~xample cotton,
by the ~pplication ~nd fixing methods customary in the
art, in particular by the applica~ion ~ondi~lons des-
cribed and employed for fiber-reactive dyes, produce~
~trong clear orange-colored dyeing~ and print~ h~ing
good light fastne~s properties and good wet fastne~s
properties, in particular good wash~ ~ulling, perspira-
tion and cross-dyeing fastne~ properties.
~ample 2
a) A solution of 39 part6 of cyanuric chloride in 150
part~ ~y volume o~ acetone is added with ~tirring to
3~0 part~ of ice; about lODO parts by volu~e of an
agueous cold, le~s than 10C, neutral ~olutio~ of
108 part6 of an aminoazo compound con~tru~ted from
4 r 6~di~ulfo-1,3~diaminobenzene as diazo ~omponent
and 2-naphthol-6-carboxylic acid ~ coupling com-
ponent ~re added with Btirring to the ~uspension.
~he batch i~ ~uh~equently ~tirred at O to 10C for
about 4 ~ore hours ~t a pH maintained between 4 and
. . . ~
.
; ~
: ~ :
. . ~ , .
~ 3 2 ~
- 13 -
5 until amine i5 virtually no longer detectable.
b) 400 parts by volume of an aqueous neutr~l ~olution
of 37 part~ of 3-~ulfoaniline are ~tirred int~ the
reaction batch prepared under a). Thereafter the
reaction mixture i8 rai6ed to a temp~rature o~ 40 to
45C in the cnur~e of 2 hour~ snd s~irred at 40 to
50C for about a further 12 hour6 while a pH between
4.5 and 5 until the acylation reaction has ended.
The novel azo compound of the formula
N ~ N L
3O35 SO;H ~
COOH
( ~ ~ 479 ~m)
isolated in the form of th~ alkali ~tal salt a~ an
electrolyte-containing orange powder. It has very good
fiber-reactive dye properties and applied to the mat~ri-
al8 m~ntioned in the description, in particular ~ellulose
fibers, for example cotton, by the application and fixing
~ethods custo~ary in th~ art, in particular the applica-
tion conditions de~cribed and employed ~or fiber-reactive
dye~, produces ~trong elear orange-~olored dyeings and
print~ having good l~ght fastn~ss properti~s and good wet
fa~tne~ propertie~, ~uch a8 in part~cular good wa~h,
fullin0, p~r~piration and ~ro~s-dyeing fastn~ss proper-
ties.
~ ple 3
Aniline-4-~ulfonîe acid îs reacked with cyanuric chloride
by the procedure o ~xample la~, and the ~nthesi~ batch
obtained i~ added with ~tirring to a ~olution of 98 parts
of 1,3 diamino~enzene~4-~ulfonic acid in ~bout 600 part~
of water at a pH betwe~n 6 and 7; the reaction mixture i~
heat~d to 40~, and ~tirrin~ i~ contlnu~d at a tempera-
..
:
. . .
- . : , , :: .: . - .
- 14 _ ~32~
ture between 40 and 45C while the pH is maintained
between 5 and 6 by maan~ of ~odium bicarbonate until the
diamino compound i8 virtually no longer detectable.
The batch obtained from this ~econd acylation reaction i~
a*mixed with 1000 parts of ice and 150 part~ by Yolume of
aqueou~ 31~ strength hydrochloric acid and diazotized
~ith an aqueous ~olution of 35 parts of sodium nitrite.
Th~ diazotization mixture i~ then added with ~tirri~g t~
a ~olu~ion of 94 part~ of 2-naphthol-6-carboxylic ac d in
about llOO parts of water and 45 part~ of aqueous ~odium
hydroxid solution at a pH between 6 and 6.5, the pH
being maintained between 4.5 and 6 throughout the entire
coupling reaction by means of ~odium bicarbonate. Stir-
-- ring i8 continued for ~ome tLme until the coupling haæ
ended.
The monoazo compound according to the ~n~ention i8
isolated in a conventi~nal manner, for example by evapor-
ating or ~pray-drying the neutral Yynthesi~ solution or
by 3alting out with an electrolyte salt, for example
potas~ium chloride. ~n electrolyte-containing red powder
i~ obtained of an alkali metal ~alt, for example pota~-
~ium salt, of the compound of the formula
Cl OH
5 ~ NH ~ N ~ NH ~ N N ~
COOH
(~max ~ 501 ~m)
whlc~ ha~ very good fiber-r~active dye properti~ and
applied to the material~ mentioned i~ the description, in
particular cellulose ~ r material~, ~uch as cotton, by
the applicati~n method~ cu~tomary in the art, produse~
~trong bri~ht red d~eings and prin~ having good light
fastne~ propertl~B and good wet a~tne~ pr~per~ies, in
- 15 ~ 3 2 ~
particular good washing, milling, per~piration and cro~s-
dyeing ~astne~s properties.
~sample 4
a) Fir~t the twofold conden~ation product i~ prepared
from cyanuric fluoride with 2~4-di~ulfoaniline and
4-~ulfo-1,3-diaminobenzene: 13.6 partæ of cyanuric
chloride ~r~ gradually added in the cour~e ~f 5 to
10 minutes with thorough ~tirring to a ~olution at
0C of the ~odium salt of 25.3 parts of 2,4-di~ul-
foaniline in 150 parts of water while maintaining a
p~ between 5 and 5.5. Stirring i~ then continued at
that temperature and that pH ~or a further 5 to 10
minutes until diazotizable amine is no l~nger
detect~ble. The cold ~olution of thi~ monocondensa-
tion product is then added with horough stirring to
a 601ution at 15 to 20C of the sodium salt of 19
p~rts of 1,3-diaminobPnzene-4-sulfonic acid in 200
part~ of water in the course of 15 to 20 minutes.
~he batch i~ subsequently stirred at a temperature
~etween 15 and 25C and at a pH between 5 and 6 for
a further hour.
~he tw~fold conden~atio~ produs~ i~ diazotized and
coupled with 2-naphthol-6-carboxylic acid in accor-
dance with the directions of ~xample lc~ and iso-
lated. The pota&~iumf60dium ~alt i~ obtained of the
compound of the formula
F OH
S03H N ~ N L
~ ~ NH ~ N ~ NH ~ N N ~/
H03S ~ S03H
COO~I
( ~ax ' 504 nm).
This ~o compound accoxding ~o the invention ha~ very
.
.
16 ~ ~ e~
good fiber-reactive dye properties and dye~ the materials
mentioned in the description, in particular wool, includ-
ing wool with a low-felting fini~h, in brilliant red
~hades with good color buildup and good fastn~ proper-
ties.
~amples 5 to 229
The Table E x~mple~ below describe further novel monoazo
compound~ conforming to the general formula (A)
I pH
N~N ~
N ~ N - D* N = N ~ ~A)
COOH
in terms of their component~. They c~n ~e prPpared in a
manner according to the invention, for example by one of
the procedure~ de~cribed ln ~xample~ 1 to ~, from he
corresponding~tarting compounds (2-naphthol-6-carboxylic
acid a~ coupling component, the diamino ~pound of the
general formula H(R)N-D-NH2, cyanuric chloride or cyan
uric fluorid~ and an amino compound conforming to the
formula R~-H). They have ~ery goQd dye properties and
produce on the material~ mentioned in the de~cription, in
particular cellulose fiber materials, for example cotton,
~nd likewise on wool, ~trong dyeing~ and prints having
good fa~tne~ propertie~ in the hue indicated in the
phrticular Table Ex~mple for dyeing~ on cot~on.
.
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