Note: Descriptions are shown in the official language in which they were submitted.
~3363~
The invention relates to the field of fiber-
reactive disazo dyestuffs.
with Publication Nos.
European Patent Applications~0,022,265 and
0,048,355 d;sclose f;ber-react;ve dyestuffs which are d;s-
azo compounds composed of 1-am;no-8-naphthol-3,6~ or
-4,6-d;sulfonic ac;d as bivalent coupling component, an
an;l;ne or aminonaphthalene compound acid-coupled thereon
as a f;rst diazo component and a phenylenediaminosulfonic
acid compound as a second diazo component to whose second
amino group is bonded a chloro~riazinyl radical which is
bonded to a fiber-reac~;ve aniline radical of the vinyl
sulfon~ seriesr
W~ have now found novel, valuable and advantageous
water-soiuble disazo compounds which hav~ the general
formula (13
. ~ S03M ~12N O~I
~ N = N ~ -N ~ ~ - D
R2 ~ Nl ~ N ~ NH ~ M03 ~ S03~i
X SO2 (13
in which
R is a hydrogen atom, an alkyl group of 1 ~o 4
carbon atoms, such as, for example~ the ethyl
group or~ in particular~ the ~ethyl group~ an alk~
oxy group of 1 to 4 carbon a~oms, such as~ for
example, the ethoxy grcup orO in particular~ the
methoxy group, or a chlorine atom,
,
~963~
R is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms,
such as, for example, the ethyl group or, in particular, the
methyl group, an alkoxy group of 1 to 4 carbon atoms, such as, for
example, the ethoxy group or, in particular, the me-thoxy group, or
a chlorine atom, and Rl and R2 can be identical to or different
from each other, R is a hydrogen atom or an alkyl group of 1 to 4
carbon atoms, such as, for example, the ethyl group or, in particu-
lar, the methyl group, an alkoxy group of 1 to 4 carbon atoms, such
as, for example, the ethoxy group or, in particular, the methoxy
group, or a sulfo group (corresponding to the general formula
-S03M where M has the meaning given below), M is a hydrogen atom
or an equivalent of a metal, preferably of a monovalent or divalent
metal, such as of an alkali or alkaline earth metal, in particular
of sodium, potassium or calcium, X is vinyl or ~-sulfatoethyl
group, Y is a chlorine atom or a fluorine atom with the proviso
that if Y is chlorine, D is a phenyl radical which can be substi-
tuted by 1, 2 or 3 substituents from the group consistlng of
carboxy, (corresponding to the general formula -COOM where M is of
the above-mentioned meaning) sulfo, alkyl of 1 to 4 carbon atoms,
2Q such as ethyl or, in particular, methyl, alkoxy of 1 to 4 carbon
atoms, such as ethoxy or, in particular, methoxy, halogen, such
as chlorine, bromine or fluorine, trichloromethyl, trifluoromethyl,
nitro, alkanoylamino having 1 to 4 carbon atoms in the alkyl
radical, such as acetylamino or propionylamino, benzoylamino which
can be substituted in the ben~ene nucleus by one or two sub-
stituents from the group consisting of methyl, ethyl, methoxy,
ethoxy, chlorine and sulfo, phenylsulfonylamino which can be
substituted in the phenyl radical by one or two substituents
,-r~
;? ., ~ -- 3
~963~
from the group consisting of methyl, ethyl, methoxy and ethoxy,
such as p-toluenesulfonylamino, and this phenyl radical D prefer-
ably contains as substituent at least one sulfo group or carboxy
group, or D is a naphthyl radical which is substituted by 1, 2 or
3 sulfo groups, and if Y is fluorine, D is phenyl unsubstituted or
substituted by 1, 2 or 3 substituents selected from the group
consisting of carboxy, alkyl of 1 to 4 carbon atoms, alkoxy of 1
to 4 carbon atoms, halogen, trichloromethyl, tri.fluoromethyl,
nitro, alkanoylamino having 1 to 4 carbon atoms in the alkyl
moiety, benzoylamino unsubstituted or substituted in the benzene
nucleus by 1 or 2 substituents selected from the group consisting
of methyl, ethyl, methoxy, ethoxy, chlorine and sulfo, and
phenylsulfonylamino unsubstituted or substituted by 1 or 2
substituents selected from the group consisting of methyl, ethyl,
methoxy and ethoxy, or D is naphthyl substituted by 1, 2 or 3
sulfo groups, provided that in compounds in which the triazinyl-
amino radical is bonded to the benzene nucleus in the meta-
position to the azo group and in the para-position to the sulfo
group -SO3M and R is hydrogen, then D is not 5-sulfo-naphth-1-yl,
1,5-disulfo-naphth-2-yl, 4,8-disulfo-naphth-2-yl, l-sulfo-naphth-
2-yl nor 3,6,8-trisu].fo-naphth-2-yl.
The above moieties (Rl, R2, R, Y and the substituents
in D) can be identical to or different from one another.
A preferred embodiment of the present invention is a
water-soluble disazo compound of the formula 11)
~ - 4 -
63~
R~ SO3M H2N OH
\,~ ¦l ~ N = N~N=N-D
R2 ~ NHJ~ ~ NH~ ~ SO3M
R MO3S
X-S02 (1)
1 2
in which R and R , identical to or different from each other,
are each a hydrogen atom, an alkyl group of 1 to 4 carbon atoms,
an alkoxy group of 1 to 4 carbon atoms or a chlorine atom, R is
a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, an
alkoxy group of 1 to 4 carbon atoms or a sulfo group, M is a
hydrogen atom or the equivalent of a metal, X is vinyl or ~-
sulfatoethyl group, Y is a chlorine atom or a fluorine atom with
the proviso that, if Y is chlorine, D is a phenyl radical which
can be substituted by 1, 2 or 3 substituents from the group con-
sisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon
atoms, halogen, trichloromethyl, trifluoromethyl, nitro,
alkanoylamino having 1 to 4 carbon atoms in the alkyl radical,
benzoylamino which can be substituted in the benzene nucleus by
one or two substituents from the group consisting of methyl,
ethyl, methoxy, ethoxy, chlorine and sulfo, phenylsulfonylamino
which can be substituted by one or two substituents from the
group consisting of methyl, ethyl, methoxy and ethoxy, carboxy
and sulfo, or D is a naphthyl radical which is substituted by
1, 2 or 3 sulfo groups, if Y is fluorine, D is monosulfophenyl
or is naphthyl substituted by 1, 2 or 3 sulfo groups and the
moieties Rl, R2, R, Y and the substituents in D can be identical
- 4a -
! y~
~' ~
to or different from one another.
The azo compounds of the invention can be in the form
of their free acid or preferably in the forrn of their salts, in
particular neutral salts; specific examples of such salts are
the alkali metal and alkaline earth metal salts, for example the
sodium, potassium or calcium salts. The new compounds are
preferably used in the form of these salts for dyeing lin the
general sense and including
4b -
~ q~
-- 5
printing~ hydroxy- and/or carboxamide-containing material,
in particular fiber material~
The presen~ invention also relates to a process
for preparing these disazo compounds of the invention,
which comprises coupling a monoazo compound of the general
formula (2)
S03M H2N OH
2~ H ~ so M
X-SO
~ (2)
in which R1, R2, R, D, M, Y and X have the abovementioned
~eanings, with ~he diazonium salt of an am;no compound o-f
the general formula (3)
~ l2N - D ~3)
;n which D has the abovementioned meaning.
The coupling reaction in the process of the inven-
tion is carried ou~ analogously to known methods, for
example in an aqueous medium at a pH-value between
3 and 9, preferably at a pH-value between ~ a-~d 7.
The monoa~o compound of the general formula (2~,
which is used as a starting compound, can be prepared ;n
a manner of the invention by reacting ~he diazon;um salt
2n of an amino compound of the general formula (4)
0
~2 ~ NH ~ N ~ NH- ~ NH2
X-S02 ' ~ j
63~
~ 6 --
in which R1, R2, R, M, Y and X have the abovementioned
meanings with 1 amino-8-naphthol-3,6- or -4,6-disuLfonic
ac;d in an acid, preferably aqueous, medium, for example
at pH 0 - 3. The d;azotization of the amine of the
general formula (4) and the acid coupling reaction can
be carried out analogously to long known methods.
Amino compounds of the general formula (4~, which
are used as starting materials, can be prepared analog-
ously to known methods, described, for example, inwith Publication Nos.
European Patent Applications~0,032,187, 0,036,133,
0~036,582 and 0,0~0,806, by reacting cyanuric chloride
or cyanuric fluoride (2,4,6-tr;chloro- or 2,4,6-trifluoro-
1,3,5-triazine? f;rst with 3n amino compound of the gene-
ra( formula (5)
1?.1 ,
~2~3 N~12
X-S02
;n which R1, R2 and X have the abovementioned meanings,
and then with a phenylened;amino compound of the general
formula (6?
SO3M
~ (6
R
20 ;n wh;ch M and R have the abovementioned meanings~
For example, the reaction of the cyanuric chloride
- 7
in the first condensation s~age with the amine of the
general fornula (5) can be carried out in an aqueous
an
medium or aqueous organic medium in the presence of~acid
acceptor, such as alkali metal or alkal;ne earth metal
S carbonates, alkal; metal or alkal;ne earth metaL hydro-
gencarbonates or hydrox;des or alkal; metal acetates - the
alkal; and alkaline earth metals preferably being sodium,
potassium or calcium -, and similarly of, for example,
tertiary amines, such as pyridine, triethylamine or quino-
10 line. The reaction te~perature chosen for preparing thisprimary condensation product ;s within the range between
-10C and ~40C, preferably between -10C and +30C, ;n
particular preferably between 0C andt10C, at a pH of from
0.7 ~0 5, preferabLy .1 to 3.
The second condensation stage, between the di-
chlorotriazinylamino compound and the phenylenediamino
compound of the general formula (6), can also be carried
out ;n an aqueous organic medium; but it ;s preferably
carr;ed out ;n an aqueous medium to which, if necessary,
an acid acceptor~ like those given above, is added~ The
reaction temperature is preferably chosen from between
10 and 60C, part;cularly preferably between Z0 and 50C,
at a pH of from 2 to 8, in particular of from 3 to 6.
The reaction of cyanuric fluoride in the first
condensation stage w;th the amino compound of the general
formula (6) is carried out analogou~ly to that of cyanuric
chloride, but preferably in an aqueous organic med;um at
a ~emperature between -10C and +20C, in particular be~een
.. . . , .. _ _ ~
0C and t10C, at a pH of from 0.7 to 3, pr.eferabiy or f~o~ 1 to 2.
. _ _ _ _ .... . . . _ . . . _ ... . .. . .. . . .
-- 8 --
Like the dichlorotriazinylamino compound, the difluoro-
~riazinylamino compound from cyanuric fluoride and the
amino compound of the general formula (S~ can also be
reacted with phenylened;amino compound of the general for-
mula (6), preferably at a reaction temperature be~Jeen
0C and -~30C, in particular between 10C and 20C, at a pH
of from 2 to 6, pre~erably of from 4 to 5. The~amin~ compounds
of the formulae (5) and (6) can, however, also be reacted
in reverse order with cyanuric chloride or cyanuric fluor-
ide, to give conpounds of the formula (4).
An example of an organic solvent which can be usedin these condensation reactions is acetone in which the
cyanuric chloride or cyanuric fluoride has been d;ssolved
beforehand; however, it is also possible to d;spense ~ith
organic solvents.
Examples of amino compounds of the general formula
(3) which can be used as starting compounds in the pre-
parat;on of d;sazo compounds according to the invention
are ~-chloroaniline, 2,4-d;chloroaniline~ 2-carboxyan;line,
3-carboxyaniline, 4-chloroaniline-2~sulfonic ac;d, 2-
chloroaniline-4-sulfonic acid, 6-chloro-3-aminotoluene-
~-sulfonic acid, 2,5-d;chloroaniline-4 sulfonic acid,
2~5-dimethoxyaniline-4-sulfonic acid~ 4-ni~roaniline, 4~
acetylaminoanil;ne-2-sulfonic acid and 3-acetylaminoani-
line-6-sulfonic acid and preferably aniline-2-sulfonic
ac;dO aniline-4-sulfonic ac;d, an;line-2~4-disulfon;c
acid and aniline-2,5-disulfonic ac;d~ and among naphthyl-
amines, for example9 1-aminonaphthalene 4-sulfonic acid~
2-aminonaphthalene-5 sulfonic acid~ 2 aminonaph~halene~
6~
g
6-sulfonic acid, Z-aminonaphthalene-7-sulfonic acid, 2-
aminonaphtllalene-3,6~disulfonic acid, 2-aminonaphthalene-
4,8-disulfonic ac;d and 2-am;nonaphthalene-3,6,~-tr;sul-
fon;c acid and preferably 2-aminonaphthalene-1-sulfonic
5 acid and 2-aminonaphthalene-1,5-disulfon;c acid.
Examples of amino compounds of the general for-
~ula (5) are 3-(~-sulfatoethylsulfonyl)-aniline, 3-vinyl-
sulfonylaniline, 2-methoxy-5-(~-sulfatoethylsulfonyl)~
aniline, 2-methoxy-5-vinylsulfonylaniline, 2,5-dimethoxy-
10 4 (~-sulfatoethylsulfonyl)-aniline and ;ts vinylsulfonyl
derivative, 2-me~hoxy-4-(~-sulfatoethylsulfonyl)-aniline
and its vinylsulfonyl derivative, 4-methoxy-5-(~-sulfato-
ethylsulfonyl)-aniline and its vinylsulfonyl derivative,
2,4-dimethoxy-5-~-sulfatoethylsulfonylaniline and its
1~ vinylsulfonyl derivative, 2-methoxy-5-methyl-4-(~-sulfato-
ethylsulfonyl)-anil;ne and ;ts v;nylsulfonyl derivative,
2-methoxy-5-chloro-4-(~-sulfatoethylsulfonyl)-aniline and
its vinylsulfonyl derivative, but preferably 4-(~-sulfato-
ethylsulfonyl)-aniline and 4-vinylsulfonylaniline.
Examples of phenylenediamino compounds of the
general formula ~6) are 1,4-diaminobenzene-2,5-disulfonic
acid, 1,4~diaminobenzene-2,6-disulfonic acid, 2,5-diamino~
toluene-4-sulfonic acid, 2~4-diaminotoluene-5 sulfonic
acid, 2,5~diaminoanisole-4-sulfon;c acid and 2,4 d;amino-
anisole-5~sulfon;c acid~ but preferably 1~3-d;aminobenzene-
4-sulfonic acid and 1,4-diaminobenzene-5-sulfonic acid~
Those compounds of the invention are preferred in
which ~he group of the formula ~S02-X is bonded to the
benzene nucleus in meta-position, ;n part;cular in para-
- 10 -
position, relat;ve to the am;no group. ~hose compounds
of the invention are also preferred in wh;ch the moiety
X represents the ~-sulfatoethyl group.
Moreover, ;n disazo compounds of the general for-
mula (1), the moiety R1 is pre~erably a hydrogen atomor a methyl group or a methoxy group or a chlorine atom,
R2 is preferably a hydrogen atom, a methyl group or a
methoxy group and R is preferably a hydrogen a~om or a
sul-fo group.
1~ Furthermore, in compounds of the ;nvention, the
moiety D is preferably a phenyl rad;cal which ;s substi-
tuted by one, two or three substituents which are sel-
ected from the group cons;sting of 2 alkoxy groups of 1
to 4 carbon atoms, 2 alkyl groups of 1 to 4 carbon atoms,
2 chlorine atoms~ 1 bromine atom, 1 fluorine atom~ 1 tri~
chloromethyl group, 1 trifluoromethyl group~ 1 alkanoyl
a~;no group having 1 to ~ carbon atoms in the alkyl rad;-
cal, 1 n;tro group, 1 carboxy group and 2 sulfo groups.
D ;s part;cularly preferably the phenyl rad;cal wh;ch is
substituted by 1, 2 or 3 substituents selected from the
group consist;ng of 2 alkoxy groups, such as, in part;cu-
lar, me~hoxy groups, 2 chlorine atoms, 2 sulfo groups,
1 carboxyl group, 1 nitro group, 1 alkyl group of 1 ~o 4
carbon atoms, such as, in particular, a Methyl group, and
1 acetylam;no group. D ;s ir, par~;cular a phenyl rad;ca~
wh;ch is subst;tuted by one or two sulfo 0roups.
D is also preferably a naphthyl radical whish ;s
subst~tuted by 1, 2 or 3 sulfo groups~
No~eworthy ind;vidual compounds are espesially
96~
the novel disazo cornpounds descr;bed in Examples 1 to 9,
13, 17, 19 and 20~
Compounds of the ~eneral -formula (1) prepared
according to the invention can be separated and isolated
5 from the synthesis solutions by generally known methods,
for example by precipitating them from the reaction medium
by means of electrolytes~ such as, for example, sodium
chloride or potassium chloride, or by evapora~ing, for
example spray~drying~ the reaction solution, to which a
10 buffer substance, such as, for example, a rnixture of
monosodium and disodium phosphates can be added. If appro-
priate, ~hese synthesis solutions, if necessary after a
buffer substance has been added and/or they have been con-
centrated, can also be used in dyeing directly as a liquid
15 formulat;on.
D;sazo compounds of the ;nvent;on have valuable
dyestuff properties which~ by virtue of the v;nylsulfonyl
or ~-sulfatoethylsulfonyl group and the halogenotriazinyl
radical, have fiber-reactive properties~ The new com-
20 pounds are preferably used for dyeing ~in the generalsense as ;nclud;ng print;ng) llydroxy- and/or carboxalnide~
containing mater;als, for example in the fc,rm of ~heet-
l;ke struc~ures, such as paper and leather or sheeting,
such as, for example, made of polyamide, or in the mass,
25 such as, for example, polyamide and polyurethane, but in
particular these ma~erials in fiber form~ ~he presen~
invention accordingly also relates to the use of co~pounds
o~ the general formula (1) for dyeing ~in the above sense~
these materials or rather to methods for dyeing such
- 12 -
materials in conventional methods ;n which a compound of
the general formula t1) ;s used as a coloran~ In these
methods the materials are preferably ;n the form of f;ber
mater;als, ;n particular in the form of textile fibers,
5 such as yarns, packages, or woven or knitted fabr;cs.
~ Iydroxy ~containin~ materials are natural, regen-
erated or synthetic hydroxy -containing materials, such
as, for example, cellulose fiber mater;als or regenera~ed
cellulos;c mater;als or polyvinyl alcohols. Cellulose
f;ber materials are preferably cottonr but also other
vege~able fibers, such as linen, hemp~ jute or ram;e
fibers; examples of regenerated cellulose f;bers are v;s-
c~se staple and filament v;scose~
Examples of carboxam;de-con~a;n;ng mater;als are
synthet;c nylons, such as nylon ~,6, nylon 6, nylon 11
or nylon ~, and polyurethanes, ;n part;cular ;n the form
of f;bers, or natural polyam;des, for example wool or
other an;mal ha;rs, s;lk or leather.
D;saz.o compounds of the ;nvent;on can be applied
and f;xed to sa;d substrates, ;n part;cular to sa;d f;ber
mater;als, by the appl;cat;on techniques known for water-
soluble dyestuffs, ;n particular for fiber-react;ve dye-
stuffs~ .
~or ;nstance, on cellulose f;bers they g;ve ;n
the exhaus~ me~hod in ~he presence of various ac;d accep-
tors and, if desired~ neutral salts, such as sodium chlor~
idè or sodium sulfate, very good color yields and excel-
lent color bu;ld~upn Dye;ng ;s carried out at ~empera-
tures between ~ and 105C~ preferably bet~Jeen 60 and
: '
a~;3~
- 13 -
100C, ;f appropr;ate at temperatures up to 120C under
pressure, ;f appropr;ate in the presence of customary
dye;ng aux;Liaries~ in an aqueous bath, by ;ntroduc;ng
the fiber material into a warm bath and gradually raising
5 this to the desired dyeing temperature and complet;ng the
dye;ng process at this temperature~ If desired, neutral
salts which accelerate the exhaus~ion of the dyestuff can
also be added to the bath only after the dyeing tempera-
ture proper has been reached~
The padding method also gives excellent color
y;elds on cellulosic fibers, on wh;ch the dyes can be
fixed ;n a customary manner by leaving the dyeing to stand
at room temperature or elevated temperature, for example
up to 60C, by steam;n3 or by means of dry heat~
S~rong pr;nts hav;ng well-delineated contours and
~ a clear white ground are also obtained in customary print-
: ing methods for cellulosic fibers~ which can be carried
out in one step - for example by printing with a print
paste containing sodium bicarbonate or a d;fferent ac;d-
b;nd;ng agent and then steaming at 100 bo 103C - or ~h'O
steps - for example by printing wi~h a neutral or weakly
acid print paste and then fix;ng either by passing the
printed goods through a hot electrolyte-conta;ning alkal-
ine bath or by overpadding w;th an alkal;ne electrolyte-
conta;ning padd;ng liquor and then leaving the material
: overpadded to stand or steaming it or ~reating ;t with
dry heat. ~ The ou~come of the prin~s is hardly depen-
:; dent on varying fix;ng conditions, if at all~ The
.. degrees of fixation obtained with the compounds o-f the
.. ..
- 14 -
;nvention not only in dye;ng but also ;n pr;nt;ng are very
h;gh~
In add;tion to customary steam at 100to 103C, ;t
is also poss;ble to use superheated steam or saturated
5 steam at temperatures of up to 160Ca In dry heat f;xing
by customary thermof;x;ng methods, hot air at 120 to 200C
is used.
Examples of the agents which bind acid and effect
the fixat;on of compounds of the invention on celLulosic
10 fibers are water-soluble basic salts of alkali metals
and also alkaline earth metals of inorganic or organic
acids or compounds which liberate alkali when heated. The
alkali metal hydroxides and aLkali metal salts of ~leak to
medium inorganic or organic acids are particularly
15 noteworthy, the sodium and potassium compounds being
intended ;n particular among the alkal; metal compounds.
Examples o, such acid-b;nding agents are sodium hydroxide,
potassium hydroxide, sodium carbonate, sodium bicarbonate,
potassium carbonate, sodium formate, sodium dihydrogen-
20 phosphate, d;sod;um hydroQenphosphate, sod;um tr;chloro-
acetate, sod;um s;l;cate and tr;sod;um phosphate.
The treatment of compounds of the invention with
acid bind;ng agencs, if appropriate under heat~ bonds ~he
compounds of the invent;on chem;cally to the cellulose
25 fiber. The cellulose dyeings, ;n particular, have excel-
len~ manufacturing and end~use fastness propercies, such
as~ in parti~ular, wet fastness propert;es, after the cus
tomary aftertreatmen~ whereby unf;xed dyestuff portions
are removed by rinsing~
~ 15 -
As regards the coloristic properties of compounds
according to the invention, ;t is particularly note~orthy
that they are distinguished by good stability in print
pastes and padding liquors, even in the presence of alka-
S lis, by very good a~finity from a long liquor, by goodcoLor build-up in customary dyeinQ and printing methods,
by an even depth of shade in the dyeing of cotton and
regenerated cellulose f;bers, by the levelness of the dye-
;ngs and prints prepared with them and also by the fact
1D that long l;quor dyeings are level i~ various amounts of
electrolyte have been added. Unfixed dyestuff portions
can be readily washed out.
Polyurethane fibers and polyamide fibers are cus-
tomarily dyed from an ac;d med;um. ~or example, acet;c
ac;d and/or ammon;um sulfate or acet;c acid and ammonium
acetate or sodium acetate can be added to the dyeba~h to
obtain the desired pH. To obtain an acceptably level
dyeing, it is advisable to add customary level;ng auxili-
aries~ such as, for e~ample, those based on a reaction
product of cyanur;c chlor;de w;th three t;mes the molar
amount of an am;nobenzenesulfonic ac;d and/or an am;no-
naphthalenesulfonic acid or ~hose based on a react;on pro-
duct of, for example, stearylamine with ethylene oxide~
The material to be dyed is generally ;ntroduced at a tem-
~5 perature of about 40C into the initially slightly alka-
line bath, and ag;tated there;n for some t;me, the dye
bath ;s brought to a weakly ac;d~ preferably weakly ace-
tic ac;d pH, and the actual dyeing is carr;ed out at a
temperature between 30 and 105C~ pre~erably between ~0
- 16 -
and 100Cn
Disazo compounds of the ;nvention are distin-
guished in the dyeing and printing of fiber materials by
a high degree of fixation, ~hich fact is economically,
5 energyw;se and ecologically of great benefit in ;ndustry,
since a h;gh ut;l;zation of the dyestuff offered by a higher
f ~ tion mgans an energy saving and easier washiny-out
of the~reduc~d)unfixed dyestuff portion~and additionally
the effluent is less polluted.
Dyeings and prints prepared ~ith disazo compounds
of the formula ~1~ are d;stinguished by bright shades.
The dyeings and prints on cellulosic fiber mater;als, in
part;cular, have, as already mentioned, a great tinctorial
strength and, furthermore, very good light fastness pro-
15 perties(not only in the dry but also in the moist stat~,
and very good fast~esses to was~ing with both peroxide-
free and peroxide containin~ detergents, to milling~ toand
water A sea~ater,and acid fastness properties, and also
very good crossdyeing fastness properties, such as, in
20 particular, very good acid crossdyeing fastness properties,
and very good persp;ration fastness properties, and also
good pleat;ng, hs~ pressing~ rubb;ng and gas fume fading
fastness properties~ They are also highly resistant ~o
chlorina~ed ~ater and copper ion donors; they are there-
25 fore compatible~ for example~ ~ith copper complex dye-
stuffs. Nor does ~he use of compounds of the invention
in dyeing cellulosic fiber ma~erials harden the hand of
the dyed material.
Neither print pastes, nor padd;n~ l;quors~ nor
f C~ 17 -
dye;n~ liquors nor unfixed prin~s or pad-dyeings wi~h com~
pounds of the invention are sensi~ive to gases which are
acid or contain sulfur dioxide~
Dyeings prepared with compounds of the invention
S have navy to black shades; they generally do not exh;bit
in art;fic;al l;ght the unfavorable, undesirable reddish
tinge which leads to the 'red even;ng shade~ since they
generally have a sl;ghtLy more green;sh t;nge. Fr,r th;s
reason the compounds of the invent;on generally have a
10 llneutral~evening shade, so that ;t is not necessary to
blend the disazo compounds of che ;nvent;on w;th a su;t-
able shading dyestuff; for dyestuffs which exper;ence a
marked sh;ft in hue under art;ficial light have the disad-
vantage that it not only restr;cts their general suit-
abil;ty for prepar;ng dye;ngs but also complicates theiruse in the preparation of dyeings when shad;ng dyestuffs
have to be added to obta;n dyeings which are reasonably
satisfac~ory when exposed to artificial l;ght, for in-
stance worn in art;f;c;al light or, qu;te generally, are
used in artificial l;ght.
The examples, wh;ch follow~ serve to illustrate
~he inventionO The compounds described by formula are
given in the form of free ac;ds; they are generally pre-
pared and isolated ;n the form of their sodium or pot-
assium sal~s, and they are used ;n the form of the;r sal~sfor dyeing. Similarly, the start;ng compounds men~;oned
;n the form of ~he free ac;d ;n the follow;ng examples~
;n particular tabled examples~ can be used in the syn-
thesis as such or in the form of .he;r sal~s, preferably
- 18 -
alkali metal salts, such as sodium or potass;um salts.
In the examples, parts are parts by we;ght and
percentages are percentages by we;ght, unless o~herw;se
stated. Parts by we;ght relate to par~s by volume as ~he
kilogram relates to the liter.
Example 1
a) A neutral solut;on of 35.1 par~s of 3-~-sulfatoethyl-
sulfonylan;l;ne ;n 130 parts of water is added with eff;-
c;ent st;rr;ng to a m;x~ure of 24 parts of cyan~r;c chlor
;de and 130 par~s of ice-waterr The react;on m;xture ;s
adjusted to pH 4 - 4.5 and held at this pH during effi
c;ent st;rr;ng for five to six hours. This batch is then
added with stirring ~o a neutral solut;on of 19~8 parts
of 1,3-diam;nobenzene-4-sulfon;c ac;d ;n 2no parts of ;ce-
wa~er~ and the result;ng m;xture ;s st;rred at pH 5 - 6
; for 10 hoursO
b) The solut;on of the secondary condensat;on product pre-
pared under a) is cooled do~n to 0C - 5C and adjusted
to pH 1 - 2 w;th hydrochlor;c ac;d, and 13D5 parts by
volume of an aqueous 40X strength sodium nitr;te solution
are added w;th st;rr;ng. 2701 parts of 1-am;no-8 naphthol-
3,6-~ lf~ni~ acid are then added portionswise to this ~ n;l~ salt
solution, and stirring is continued at a pH between
1.5 and 2 for 10 to 15 hours until the coup-
25 ling react;on has ended~
c) An aqueous suspens;on of the conventionally prepared
d;azon;um salt of 15.6 par~s of an; l;ne~4-sulfonic ac;d
is added to the solution of the monoazo compound prepared
,'~
~ under b), and th;s coupl;ng ba~ch ;s adjus~ed ~o pH 6 - 7
63~
- 19 -
and stirred for about 1 to 2 hours untiL the coupling
has ended.
The synthesis solution ;s clarified in a customary
manner (addition of kieselguhr, followed by filtration)
5 and evaporated to dryness or spray-dried. This gives 1$0
parts of a black powder which, ;n addition to electrolyte
salts~ such as sod;um chLoride, contains about 50% of an
alkali metal saltO such as the sodium salt, of the com-
pound of the formula
Cl
N ~12N OI~
n ~ ~I J ~N~ - N~ = N ~ N = ~_ ~
~3~ ~ `S03H S0311
2 C~I2-CH2-OS03~ ~103S
Th;s disazo compound of the invention has very good fiber-
reactive dyestuff properties and, when applied and fixed
by the methods customary in industry for fiber-reactive
dyestuffs, gives on the materials mentioned in the descrip-
~ive section, such as, in particular, cellulose fiber
materials, strong navy to black dyeings and prints of
good to very good in-use and processing fastness pro-
perties, of ~hich the following are particularly note~
worthy: light fastness properties on dry or moist fiber
material, wash fastness properties (at 60 and 95C)~ fast~
ness to soda boiling, milling, seawater~ rubbing, gas fume
fad;n~, hot pressing, water (heavy duty~ and acid cross-
dy'e;ng and persp;ration. The dyeings and prints are
largely shade-stable to copper ion donors and chlorinated
wateru
- 20
Rfter the clar;fy;ng f;ltration~ the synthesis
solution of the novel disazo compound obtained in this
example can also be partially evaporated to g;ve a very
concentrated solution, since the novel compound is readily
soluble in water. This solution can advantageously be
adm;xed with customary buffer substances for stabiliz;ng
a pH between 3 and 7, and also dispersants and customary
suitable, water-misc;ble solvents, such as sulfolane,
dimethyl sulfoxide or ethylene glycol dimethyl ether.
The concentrated solutions thus obtained can advantage-
ously be used instead of the powders for making up dyeing
solutions and pr;n~ pastes ;n dyeing and print;ng. They
g;ve the abovement;oned navy to black dyeings and prints
;n the same qual;ty.
Example 2
a) 16.5 parts of cyanuric fluor;de are added w;th effic;ent
stirring in the course of 10 minutes to a neutral solu-
~ion of 31 parts of 4-~-sulfa~oethylsulfonylan;line in
120 parts of ;ce-water. The batch is stirred at pH 2 - 3.5
for 30 m;nutes, and i5 then admixed with a neutral solu-
t;on of 1~.8 parts of 1,3-diaminobenzene-4-sulfon;c ac,d
;n 200 parts of ice water; the batch is then stirred at
pH 4~5 - 6 for some hours.
b) The solut;on of this secondary condensation product is
then cooled down to 0 to 5C, adjusted to pl~ 1 - 1.5
w;th dilute sulfuric acid and d;azctized by adding 13.5
parts by volume of an aqueous 40% strength sodium nitrite
solu~;on~ This diazotization batch is s~irred for 3 hours,
and excess nitri~e is destroyed in a cus~omary manner by
-
add;ng am;dosulfon;c ac;d. The d;a20n;um salt suspens;on
thus prepared ;s then admixed w;th 2807 parts of 1-am;no-
8-naphthol-4,6-d;sulfon;c ac;d, and this coupling batch
;s st;rred at pH 1 - 2 for 10 hours~
5 c) The solut;on of ~he monoa~o compound prepared under b)
in th;s example is adm;xed w;th an aqueous solution of a
convent;onally prepared d;azon;um salt of 25.3 parts of
anil;ne-2,5-d;sulfon;c ac;d; the coupl;ng react;on ;s com-
pleted at pH 6 - 8 ;n the course of about 1 tO 2 hours,
10 and the result;ng solution of the disazo compound of the
invention is then adjusted to pH 5. It is convention-
al(y clarified and evaporated to dryness or spray-dried.
The disazo compound of ~he invent;on can also be salted
out from the synthes;s solut;on w;th potassium chloride,
15 and ;solated.
This gives a blu;sh black electrolyte-contain;ng
powder of an alkali metal salt~ such as the sodium or pot-
ass;um sal~, of the compound of the formula
Cl
N ~ N ~12N OEI lSO3
NII ~ `N ~ -NH ~ - N = N ~ ~ \~ N = N -
l2 ~ ~ So3~ J ~ So~
CH2 CH2-OS03H ~03S ~03~I
O
Th;s disa~o compound of ~he ;nven~;on has very good fiber-
reactive dyestuff proper~ies and, when applied ~o the
mater;als mentioned in the descr;p~;ve section, such as,
in part;cular, cellulose f;ber mater;als~ by the applica
~;on and f;xing methods customary in ;ndus~ry, ;n par~i-
cular for f;ber~react;ve dyestuffs, g;ves s~ron~ redd;sh
3~3
-- 22 --
navy to black dyeings and prints having excellent we~
fastness properties, such as, for example, a very good
wash Fastness at 6ûC and 95C, a very good acid
~ross-dyeing fastness, very good perspiration fastness
5 propert;es and a very good fastness to gas fume fading~
~xamples 3 to 200
~ he tabled examples which follo~l describe o~her
novel disazo compounds by means of their components (the
phenylenediamino compound of the general formuLa ~6),
10 cyanur;c chloride, referred to as (A)~ or cyanuric fluor-
ide~ referred to as tB), and the am;no compound of the
generaL formula (53 as components of the first diazo com-
ponent of ~he general formula (4) and the amino compound
D-NH2, which corresponds to the general formula (3), as
15 2nd dia7o component, and 1-amino-8-naphthol-3,~- and -4,6-
disulfonic acid as a bivalent coupling component cf ~he
monoazo compound of the above formula (2), characterized
in the tabled example by the pos;tion of the one sulfo
group in 3- or 4-posit;on). They can be prepared from
2D these components ;n the manner of the invention, for
example analogously to the above Working Examples.
They have very good fiber-reactive dyes~uff properties
and, when applied to the materials mentioned in the de-
script;ve section~ such as, in par~icular~ cellulose fiber
25 mater;als, by the appl;cat;on methods customary in indus-
try in dye;~g and pr;nting~ preferably by the appl;cation
and f;x;ng methods for fiber-reactive dyestuffsO give
strong dyeings and prints having good fastness properties
and ~he hue g;ven in the part;cular tabled example~
FX- Phenylene Cyanuric Amino Posi~ion Amino compound /3) ~e is navy
ample diamine (6) halide com~ound (5) of the on~ of the general
sulfo group formula D-NH2
3 1,3-diamino- (A) 4-6-sulfatoethyl- 3 2,4-disulfoaniline (greenish)
ben~ene-4- sulfonylaniline
- sulfonic acid
4 dirto(A) ditto 3 2,5-disulfoaniline tneutral)
ditto(A) ditto 3 2-sulfoaniline tneutral)
6 ditto(A3 ditto 3 3-sulfoaniline tneutral)
7 ditto(A) ditto 3 4-çhloro-2-sulfoaniline (neutral)
8 ditto(A) ditto 3 4-methoxy-2-sulfoaniline ~greenish)
9 ditto. ~A) ditto 3 2-chloro-4-sulfoaniline ~greenish)
ditto~A) ditto 3 2,5-dimethoxy-4-sulfoaniline ~greenish~
11 ditto~A) ditto 3 3-carboxyaniline ~neutral)
12 ditto~A) ditto 3 4-acetylamino-2-sulfoaniline ~greenish)
13 ditto(A) ditto 3 1,5-disulTo-2-naphthylamine (greenish)
14 ditto~A) ditto 3 3,6-disulfo-2-naphthylamine ~greenish)
-15 dit~o~A) ditto 3 4,8-disulfo-2-naphthylamine ~greenish)
16 ditto~A) ditto 3 3,6,8-trisulfo-2-naphthylamine ~greenish)
17 ditto~A~ ditto 3 1-sulfo-2-naphthylamine (greenish)
18 ditto(A) ditto 3 6-sulfo-2-naphthylamine ~greenish)
- 19 ditto~A) ditto 3 -- 4-sulfo-1-naphthylamine (greenish)
ditto~A) 4-vinylsulfonyl~ 3 4-sulfoaniline ~greenish)
aniline
21 ditto(A) ditto 3 2,4-disulfoaniline ~neutral)
Ex- Phenylene- Cyanuric Amino Pos;tion Am;no compound ~3) Hue is navy
ample diamine t6) haL;de csmpound ~5~ of the one of the general
sulfo group formula D-NH2
22 1~3-diamino- (A) 4-vinylsulfonyl- 3 2,5-disulfoaniline (greenish)
benzene-4- aniline
sulfonic acid
23 ditto (A) ditto 3 1,5-disulfo-2-naphthylamine (greenish)
24 ditto (A) ditio 3 3,6-disulfo-2-naphthylamine ~greenish)
ditto (A) ditto 3 3,6,8-trisulfo-2-naphthylamine (greenish~
26 ditto (A3 ditto 3 1,5,7-trisulfo-2-naphthylamine (greenish)
27 ditto (A) ditto 3 4,6,8-trisulfo-2-naphthylamine (greenish)
28 ditto (A) ditto 4 4-sulfoaniline (reddish)
29 ditto (A) ditto 4 2,4-disulfoaniline (neutral)
ditto (A) ditto 4 2,5-disulfoaniline (reddish) ~e
31 ditto (A) ditto 4 1 "-disulfo-2-naphthylamine (neutral)
32 ditto (A) ditto 4 3,6-disulfo-2-naphthylamine (neutral)
33 ditto (A) ditto 4 4,8-disulfo~-naphthylamine (neutral)
34 ditto (A) ditto 4 6,8-disulfo-2-naphthylamine (neutral)
ditto (A) ditto 4 - 1,5,7-trisulfo-2-napthylamine (neutral)
36 ditto (A) ditto 4 3,6,8-trisulfo-2-naphthylamine (neutral)
37 ditto (A) ditto 4 4,6,8-trisulfo-2-naphthylamine (neutral~
38 ditto (A) 4-~j-sulfatoethyl- 4 - 4-sulfoaniline (reddish)
- sulfonylaniline
39 ditto (A) ditto 4 2-carboxyaniline (reddish)
ditto (A) ditto 4 2,4-disulfoaniline (neutral)
41 ditto ~A) ditto 4 2,5-disulfoaniline (reddish)
EX- Phenylene- ~yanuric Amino Position Amino ~ompound ~3) Hue is navy
- ample d;am;ne (6) halide compound (5) of the one of the general
sulfo group formula D-NH2
42 1~3-diamino- (A) 4-B-sulfatoethyl- 4 2-sulfoaniline (reddish)
benzene-4- sulfonylan;line
- sulfonic acid
43 ditto (A) ditto 4 3-sulfoaniline (reddish)
~4 ditto (A~ ditto 4 4-carboxyaniline (neutral)
ditto (A) ditto 4 4-chloro-Z-sulfoaniline (neutral)
-46 ditto (A) ditto 4 4-acetylamino-2-sulfoaniline tneutral)
47 ditto (A) ditto 4 1-sulfo-2-naphthylamine (neutral)
48 ditto (A) ditto 4 6-sulfo-2-naphthylamine (neutral)
49 ditto (A) ditto 4 1,5-disulfo-2-naphthylamine (neutral)
ditto (A) dittG 4 4,8-disulfo-2-naphthylamine (neutral) C~
51 ditto (A) ditto 4 6S8-disulfo-2-naphthylamine (neutral)
52 ditto (A~ ditto 4 1,5,7-trisulfo-2-naphthylamine (neutral)
53 ditto (A) ditto - 4 3,6,8-trisulfo-2-naphthylamine (neutral)
54 ditto (A) ditto 4 4-sulfo-1-naphthylamine (greenish)
1,4-diamino- (A) ditto 3 4-sulfoaniline (greenish)
benzene 2-
sulfonic acid
56 ditto (A) ditto 3 2,5-disulfoaniline (greenish)
57 di-t~o (A) ditto 3 4-sulfo-1-naphthylamine (greenish)
58 -ditto (A) ditto 3 1,5-disulfo-2-naphthylamine (greenish)
59 ditto (A) ditto 3 1,5,7-trisulfo-2-naphthylamine (greenish)
ditto (A) ditto 3 2-sulfoaniline (greenish)
Ex~ Phenylen~- ~yanuric Amino Position Amino compound ~3) Hue is navy
amp~e diamine (6) halide compound (5) of ~he one of the general
sulfo group formula D-NH2
61 1~3-diamino- (A) 4-~-sulfabo~ _ 3 4-sulfoaniline ~neutral)
benzene-4,6- ethylsulfony~ani
disulfonic acid line
6Z ditto (A) ditto 3 2,4-disulfoaniline (greenish~
63 ditto (A) ditto 3 Z-carboxyaniline (neutral)
64 ditto tA) ditto 3 4-carboxyaniline (greenish)
ditto (A) ditto 3 2-chloroaniline (neutral)
66 ditto (A) ditto 3 4-chloro-2-sulfoaniline (neutral)
67 clitto (A) ditto 3 1-sulfo-2-naphthylamine (greenish)
68 ditto (A) ditto 3 1,5-disulfo-2-naphthylamine (greenish)
69 ditto (A) ditto 3 6-sulfo-2-naphthylamine (greenish) p~
ditto (A) ditto 3 Z,5-dichloro-4-sulfoaniline (greenish)
71 ditto (A) ditto 3 2,5-dimethoxy-4-sulfoaniline (sreenish)
72 1~4-diamino- (A) ditto 3 4-sulfoaniline (greenish)
benzene-2,5-
disulfonic
acid
73 ditto (A) ditto 3 2-carboxyaniline (greenish)
74 ditto (A) ditto 3 4-carboxyaniline (greenish)
ditto (A) ditto 3 2-chloroaniline (greenish)
76 ditto (A) ditto 3 2-sulfoaniline (greenish)
77 dit~o (A) ditto 3 4-sulfo-1-naphthylamine (greenish)
78 ditto (A) ditto 3 1-sulfo-2-naphthylamine (greenish)
Ex- Phenylene- Cyanuric Amino Position Amino compound (3) Hue is navy
ampie diamine (6) ~alide compound (5) of the one of the general
sulfo sroup formula D-N~2
79 1,4-diamino- (A) 4-B-sulfato- 3 6-sulfo-2-naphthylamine (greenish)
benzene-Z,S- ethylsulfonyl-
disulfonic aniline
acid
~0 ditto SA) ditto 3 1,5-disulfo-2-naphthylamine (greenish~
81 1,4-diamino- (A) ditto 3 4-sulfoaniline (sreenish)
benzene-2,6-
disulfonic
acid
82 ditto(A) ditto 3 2-sulfoaniline - (greenish)
83 ditto(A) ditto 3 2-carboxyaniline (greenish)
84 ditto(A) ditto 3 2-chloroaniline (greenish)
ditto(A) ditto 3 4-acetylamino-3-sulfoaniline (greenish)
86 ditto(A) ditto 3 4-sulfo-1-naphthylamine (greenish)
87 ditto~A) ditto 3 1-sulfo-2-naphthylamine (greenish)
88 ditto(A) ditto 3 6-sulfo-2-na~hthylamine (greenish)
89 ditto. (A) ditto 3 6,8-disulfo-2-naphthylamine (greenish)
ditto(A) ditto 3 1,5-disulfo-2-naphthylamine (greenish)
91 1,4-diamino- (A) ditto 4 4-sulfoaniline (greenish)
benzene-2-
sulfonic acid
92 ditto(A) dit~o 4 2,5-disulfoaniline (greenish)
93 ditto(A) ditto 4 2-sulfoaniline (greenish)
94 ditto(A) ditto 4 1,5-disulfo-2-naphthylamine (greenish)
Ex- Pheny(ene- Cyanuric Amino Posit;on Amino compound (3) Hue is navy
ample diamine (6) halide compound (5) of the one of the general
sulfo group formula D-NH2
95 1,4-diamino- (A) 4-~-sulfato- 4 4-sulfo-1-naphthylamine (greenish)
benzene-2- ethylsulfonyl-
sulfonic acid aniline
96 ditto (A) ditto 4 Z-sulfoaniline (greenish)
97 1,3-diamino- ~A) ditto 4 4-sulfoaniline (reddish)
benzene-4,6- -
disulfonic
acid
98 ditto (A~ ditto 4 4-sulfo-1-naphthylamine (neutral)
- 99 ditto (A) ditto 4 1~5-disulfo-2-naphthylamine (neutral)
100 ditto ~A) ditto 3 1-sulfo-2-naphthylamine (neutral) ~
101 ditto (A) ditto 3 2,4-disulfoaniline (reddish) Gg
102 ditto (A) ditto 3 2-chloroaniline (reddish) t~
103 1,4-diamino- (A) ditto 4 4-sulfoaniline (greenish)
- benzene-2,5-
disulfonic
acid
104 ditto (A) ditto 4 3-sulfoaniline (neutral)
105 ditto (A) ditto 4 2-sulfoaniline (neutral)
106 ditto ~A) ditto 4 1-sulfo-2-naphthylamine (greenish)
107 ditto (A) ditto 4 - 1,5-disulfo-2-naphthylamine (greenish)
108 ditto (A) ditto 4 2-chloroaniline (neutral)
109 1,4-diamino- (A) ditto 4 4-sulfoaniline (neutral)
benzene-2,6-
disulTonic
acid
Ex- Phenylene- Cyanuric Amino Position Am;no compound (3) Hue is n2vy
a~ple diamine (6) halide compound (5) of the one of the general
sulfo group formula D-NH2
110 1,4-diamino- (A~ 4-~-sulfato- 4 2-sulfoaniline (neutral)
benzene-2,6- ethylsulfonyl-
disulfonic aniline
acid
111 ditto (A) ditto 4 4-sulfo-1-naphthylamine (greenish)
112 ditto (A~ ditto 4 1,5-disulfo-Z-naphthylamine tgreenish)
113 2,5-diamino- (A~ ditto 3 4-sulfoaniline (greenish)
toluene-4 ~
sulfonic acid `O
114 ditto (A) ditto 3 2-sulfoaniline (greenish)
115 ditto (A) ditto 3 1-sulfo-2-naphthylamine (greenish)
116 ditto (A) ditto 3 1,5-disulfo-2-naphthylamine (greenish) ~ç
117 2,4-diamino- (A) ditto 3 4-sulfoaniline (neutral) ~:
~oluene-5- -
sulfonic acid
11~ ditto (A) ditto 3 2,5-disulfoaniline (neutral)
119 ditto ~h) ditto 3 1,5-disulfo-2-r,aphthylamine (neutral~
120 ditto (A) ditto 3 3,6-disulfo-2-naphthylamine (r,eutral)
121 Z,5-diamino- (A) ditto 3 4-sulfoaniline (greenish)
anisole-4-
sulfonic acid
122 d;tto (A) ditto 3 1,5-disulfo-2-naphthylamine (greenish)
123 ditto (A) ditto 3 2,5-disulfoaniline (greenish)
124 ditto (A) ditto 3 2,4-disulfoaniline (greenish)
Ex- Phenylene~ ~yanuric Am;no Posit;on Amino compound (3) Hue ;s navy
ample diamine (6~ halide compou~d (53 of the one of the general
sulfo group formula D-NH2
12~ 2,4-diamino- tA) 4~ sulfato- 3 4-sulfoaniline ~neutral)
anisole-5- ethylsulfonyi-
sulfonic acid aniline
126 ditto ~A) ditto 3 1,5-disulfo-2-naphtylamine(neutral)
127 ditto (A) ditto 3 1~5,7-trisulfo-2-naphthylamine (greenish)
128 1~3-diamino- (A) 3-~-sulfato- 3 4-sulfoaniline (neutral)
benzene-4- ethylsulfonyl-
sulfonic acid aniline
129 ditto (A) ditto 3 2-sulfoaniline (neutral) w
130 ditto (A) ditto 3 2,4-disulfoaniline ~neutral)
131 ditto (A) ditto 3 2,5-disulfoaniline (neutral)
132 ditto (A) ditto 3 1,5-disulfo-2-naphthylamine(greenish~
133 ditto (A) ditto 3 4,8-disulfo-2-naphthylamine(greenish)
134 ditto (A) ditto 3 4-sulfo-1-naphthylamine (greenish)
135 ditto (A) 2-methoxy-4-~6-sul- 3 4-sulfoaniline (neutral)
fatoethylsulfonyl)~
aniline
136 ditto (A) ditto 3 2,5-disulfoaniline (neutral)
137 ditto (A) ditto 3 4-sulfo~-naphthylamine (greenish)
138 ditto (A) ditto 3 1,5-disulfo-2-naphthylaminegreenish)
13q ditto (A) 2-methoxy-5-~-sul- 3 2-sulfoaniline (neutral)
fatoethylsulfonyl~-
aniline
140 ditto (A) ditto 3 2,4-disulfoaniline (neutral)
141 ditto (A) ditto 3 4-sulfo-1-llaphthylamine (greenish)
Ex- Phenylene- Cyanuric Amino ~osit;on Amino conpound t3) Hue is navy
ample diamine ~6) halide compound ~5) of the one of the general
sulfo grGup formula D-NH2
142 1,3-diamino- (A) 2-methoxy-5- ~-sul- 3 1,5-disulfo-2-naphthylamine (greenish)
benzene-4- fatoethylsulfonyL)-
sulfonic acid aniline
143 ditto (A) 2-methoxy-5-methyl- 3 4-sulfoaniline (neutral)
4- ~-sulfatoethyl-
sulfonyl)-aniline
144 ditto (A) ditto 3 2,5-disulfoaniline (neutral)
145 ditto (A) ditto } 4-sulfo-1-naphthylamine (greenish)
146 ditto (A) ditto 3 1,4-disulfo-2-naphthylamine (sreenish)
147 ditto (A) 2,5-dimethoxy-4- 3 2-sulfoaniline (neutral)
~-sulf~toethylsul- ~
fonyl) aniline CD
14~ ditto (A) ditto 3 4-sulfoaniline (neutral)
149 dit~o (A~ ditto 3 2,5-disulfoaniline (neutral) 2
150 ditto (A3 ditto 3 1,5 disulfo-2-naphthylamine (greenish)
151 ditto (A) ditto 3 - 4-sulfo-1-naphthylamine (greenish)
152 ditto ~A) 2-methoxy-5-chloro- 3 2-sulfoaniline (neutral)
4- ~-sulfatoethyl-
sulfonyl)-aniline
153 ditto (A) ditto 3 4-sulfo-1-naphthylamine (sreenish)
154 ditto (A) ditto 3 -- 2,5-disulfoaniline (neut al)
155 ditto (A) ditto 3 1,5-disulfo-2-naphthylamine (greenish)
156 ditto (A) 4-methoxy-5- ~-sul- 3 4-sulfoaniline (neutral)
fatoethylsulfonyl)-
aniline
Ex~ Phenylene Syanuric Amino Position Amino compound (3) Hue ;s navy
ample diamine (6~ halide compound (5) of the one of the general
sulfo group formula D-NH2
157 1,3-di am ino- (A) 4-methoY~y-S- ~- 3 2-sulfoaniline (neutral)
benzene-4- sulfatoethylsul~
sulfonic acid fonyl)-aniline
158 ditto (A) ditto 3 2,5-disulfoaniline (neutral)
159 ditto (A) ditto 3 1,5-disulfo-2-naphthylamine (greenish)
160 ditto (A) 2-methoxy-5- ~- 4 2-sulfoaniline (neutral)
sulfatoetnylsul-
fonyl)-aniline
161 ditto (A) ditto 4 2,4-disulfoaniline (neutral)
162 ditto (A) ditto 4 1,5-disulfo-2-naphthylamine (neutral)
163 di~to (A) ditto 4 4-sulfo-1-naphthylamine (greenish)
164 ditto (A) 2-methoxy-5-vinyl- 4 2,5-disulfoaniline (reddish) ~
sulfonylaniline ~`
165 ditto (A) ditto 4 1,5-disulfo-2-naphthylamine (neutral)
166 ditto (B) 4-~3-sulfatoethyl- 3 4-sulfoaniline (neutral)
sulfonylaniline
167 ditto . (B) ditto 3 1j5-disulfo-2-naphthylamine (greenish)
168 ditto (B) 4-vinylsuifonyl- 3 2,5-disulfoaniline (neutral)
aniline
169 ditto (B) ditto 4 ditto (reddish)
170 ditto (8) ditto 4 4-sulfoaniline (reddish)
171 ditto (B) ditto 4 1,5-disulfo-2-naphthylamine (neutral)
172 ditto (B, 3-6-sulfatoethyl- 4 2-sulfoaniline (reddish)
sulfonylaniline
Ex- Phenylene- Cyanur;c Am;no Position Amino compound (3) . Hue ;s na~y
amole diamine (6) halide compound (5) of the one of the general
sulfo group formula D~NH2
173 1,3-diamino- (B) 3-B-sulfatoethyl- 4 1,5-disulfo-2-naphthylamine (neutral)
benzene-4- sulfonylaniline
sulfonic acid
174 ditto (B) ditto 3 ditto (greenish)
175 ditto (B) ditto 3 4-sulfoaniline (neutral~
176 ditto (B) 2-methoxy-5~B- 3 ditto (neutral)
sulfatoethylsul-
fonyl)-aniline
177 ditto (B) ditto 3 1,5-disulfo-2-naphthylamine (greenish) w p~
178 ditto (B) ditto 4 ditto (neutral) t~
179 ditto ~B) ditto 4 2-sulfoaniline (reddish)
18~ ditto (~) ditto 4 2,5-disulfoaniline (reddish)
181 ditto (B) 4-methoxy-5-(B- 4 ditto (reddish)
sulfatoethylsuL-
fonyl)-aniline
182 ditto (B) ditto 4 1,5-disulfo-2-naphthylamine (neutral)
183 ditto (B) ditto 3 ditto (greenish)
184 ditto(B) 2-methoxy-4-~B- 4 4-sulfoaniline (reddish)
sulfatoethylsul-
fonyl)-~hi1in~
185 ditto(B) ditto 3 - 1,5-disulfo-2-naphthylamine (greenish-)
18G dit o(B) 2-methoxy-5-methyl- 3 ditto (greenish)
4-~ -sulfatoethyl-
sulfonyl)-aniline
187 ditto(B) ditto 3 4-sulfoaniline (neutral)
Ex- Phenylene Cyanuric Amino Pos;tion Amino compound (3) Hue is navy
ample diam;ne (6~ halide compound (5) of the one of the general
sulfo group formula D-NH2
188 1,3-diamino- (B~ 2,5-dimethoxy- 3 4-sulfoaniline (neutral)
benzene-4- 4- ~-sulfatoethyl-
sulfonic acid sulfonyl)-aniline
189 ditto (B) ditto 3 1,5-disulfo-2-naphthylamine (greenish)
190 1,4-diamino- (B) 4-~-sulfatoethyl- 3 1,5-disulfo-2-naphthylam-ne (greenish)
benzene-5- sulfonylaniline
sulfonic acid
191 ditto - (B) ditto 3 4-sulfoaniline (greenish)
192 1,3-diamino- (B) ditto- 3 ditto (neutral)
benzene-4~6- w
disulfonic
acid
?93 ditto (B) ditto 3 1,5-disulfo-2-naphthylamine (greenish)
194 1,4-diamino- (B) ditto 3 ditto (greenish)
benzene-2,5-
disulfonic
acid
195 ditto (B) ditto 3 4-sulfoaniline (greenish)
196 1,4-diamino- ~B) ditto 3 ditto (greenish)
benzene-2,6-
disulfonic
acicl
157 2,5-diamino- (B) ditto 3 ditto (greenish)
ioluene-4-
sulfonic acid
198 2,4-diamino- (B) ditto 3 ditto (reddish)
toluene-5-
sulfonic acid
Ex- Phenylene- Cyznuric Amino Posit;on AminQ compound (3) Hue is navy
am~le diamine (6) halide compound t5) of the one of the general
sulfo group formula D-NH2
199 2 5-diamino- (B) 4-~-sulfato- 3 4-sulfoaniline (greenish)
anisole-4- ethylsulfonyl-
sulfonic acid aniline
200 2 4-diamino- (8) ditto 3 ditto (neutral)
anisole-5-
sulfoniç acid
I
~,
