Note: Descriptions are shown in the official language in which they were submitted.
With the prsent invention, novel water-soluble dyestuffs of the
general formula (1)
y
X - 02S - D - N = N - Kl ¦ ~ ~ ~ K2 ~ N = N - D - SO2-X ( )
R2 R2
and their heavy metal complex compounds have been found.
The novel dyestuffs of the formula (1) can be in the form of the
free acid or in the form of their salts. They are preferably in the form of
-the salts, especially the alkali metal and alkaline earth metal salts and in
particular in the form of the sodium, potassium and calcium salts. They are
preferably used in -the form of the alkali metal salts for dyeing and printing
fiber materials.
In the above formula (1), the various radicals in the formula have
the following meaning: Kl and K2 are identical or different and Kl represents
one of the radicals of the formulae
H~ NH- HO NH-
HO3S SO3H 3 ~
SO3H
~H OH
3 NH- HO3S ~ ~ SO H
,OH OH NH-
HO3S ~ ~ NH- ~ and
SO3H
- 1 -SO3H
C ~
.
a nitrogen atom or oxygen atom, such as, for example a morpholine, piperidine
or piperazine ring.
The two radicals
~1
R2
can be identical or different in the general formula (l); prefer-
ably they are identical.
Here and in the text which follows, the term "lower" used in the
definitions denotes that the alkyl or alkylene radical contained in the group
consists of 1 - 4 C atoms.
The present invention also relates to heavy metal complex dyestuffs
of the abovementioned formula (1), in which one or both of the Rls represent
a hydroxy group and withthe hydroxy groups of the coupling component or com-
ponents bond the metal as a complex. The heavy metal complex dyestuffs are
preferably those in which two heavy metal equivalents are each bonded in com-
plex form to one molecule of the formula (1), specifically in each case to
the hydroxy groups Rl and those of the aminonaphthol-disulfonic acid radicals.
Preferred heavy metal complex dyestuffs are the copper, cobalt and chromium
complex dyestuffs of the formula (1) according to the invention, especially
the copper complex dyestuffs.
The present invention also relates to a process for the manufacture
of the novel dyestuffs of the formula (1), which comprises reacting 2 moles
of the diazonium compound of one or two aromatic amines, preferably a single
aromatic amine of the general formula (2)
C
:. ,, . : .
. '
X - S02 - D - NH2 (2)
in which D, Rl, R2 and X are as defined above and Rl is in the ortho-position
relative to the amino group, with 1 mole of a coupling component of the gen-
eral formula (3)
N ~ N ~3)
H-Kl ~ " L _ - K -H
in which Kl, K2 and Y are as defined above.
The present invention also relates to a process for the manufacture
of the heavy metal complex dyestuffs of the above mentioned general formula
(1), which comprises reacting the metal-free dyestuffs of the formula (1) in
which Rl represents a hydrogen atom or a hydroxy or lower alkoxy group, if
desired immediately following the above mentioned procedure, according to
the invention, for the manufacture of these metal-free dyestuffs of the for-
mula (1), in a manner which is in itself known, if appropriate in the pres-
ence of an oxidizing agent, with a metal donor.
The metal-free dyestuffs of the formula (1) or their heavy metal
complexes can, however, also be manufactured in a manner according to the
invention by subJecting one mole of each of the monazo compounds of the gen-
eral formulae(4) and (5)
Il
X _ 02S ~ D - ~ = N - K3 (4)
'
. ~ ~
X _ S2 ~ D - N = N - K4 (5)
descri.bed in the form of the free acids, in which Rl, R2, D and X are as de-
fined above and K3 denotes one of the radicals of the following formulae
HO NH2 HO NH2 OH
H035 503H 3 ~03H 3 N~2
HO Hp H NH2
~ H2 ~ ~
H03S J ~ S03H H03 ~ NH2 or ~ 03H
and K4 denotes one of the radicals O-r the following formulae
OH OH Hn N
~ 2
H03 ~ 3 ~ ~ NH2 ~
S03H
U~ _NH2 or ~OH
H03S S03H H03S ~ NH2
S03H
or two moles of their heavy metal complex compounds in which Rl is a hydroxy
group, preferably the 1:1 copper complex compo~mds, or 1 mole of these heavy
metal complex compounds of the formula (4) or (5) and 1 mole of the metal-
free compound of the formula (5) or, respectively, (4) to a condensation re-
action with a halogeno-s-triazine compound of the formula (6)
C
6~
N ~ N
l-lal ~ ~ ~ llal
in which Y is as defined above and Hal represents a chlorine, bromine or
fluorine atom, and, if desired, subsequently reacting the product in a man-
ner which is in itself known, if appropriate in the presence of an oxidizing
agent, with an agent which donates a heavy metal cation. These reactions
are preferably carried out in aqueous solution, optionally in the presence
of organic solvents, at room temperature (15-25 C) or elevated temperature
(up to 120 C) in accordance with known processes in an analogous manner well
known to those skilled in the art. If the heavy metal complex dyestuffs ac-
cording to the invention are manufactured by subsequent metallization, asindicated here, one or both of the Rls can be a hydrogen atom, a hydroxy
group or a lower alkoxy group.
It is also possible, in a manner according to the invention, to
convert a heavy metal complex dyestuff according to formula (1) into a heavy
metal dyestuff according to the invention which contains a different heavy
metal central atom, by splitting the original heavy metal atom from the com-
plex dyestuff analogously to the known methods (see, for example, Angew.
Chem. 64, 397 (1952)) and reacting the resulting o,o'-dihydroxy-azo dyestuff
with an agent which supplies the other heavy metal atom. Thus, for example,
copper complex dyestuffs of the formula (1) can be converted to the corre-
sponding chromium or cobal-t complex dyestuffs of the formula (1).
Preferred dyestuffs, according to the invention, of the formula (1)
and their heavy metal complexes are those in which D represents a benzene
nucleus and also those in which D represents a naphthalene nucleus, in which
the azo group is bonded in the ~-position of this naphthalene nucleus. Fur-
ther preferred dyestuffs according to the invention are those in which Y
-- 5 --
C
P6~
denotes a halogen atom, preferably a chlorine atom. Furthermore, dyestuffsof particular importance are those in which Kl represents the above men-
tioned divalent radical of l-amino-naphthol(8)-3,6-disulfonic acid, l-amino-
naphthol(8)-4,6-disulfonic acid or 2-amino-naphthol-(5)-7-sulfonic acid and
K2 represents the above mentioned divalent radical of 2-amino-naphthol(8)-6-
sulfonic acid or 2-amino-naphthol(5)-7-sulfonic acid.
In addition to the said halogen atoms and the sulfonic acid group,
the following individual groups are to be singled out for the substituent Y
in the triazine ring of the dyestuffs of the formula (1) or of the compounds
Of the formulae (3) and (6):
_O-CH3, -O-C2H5, O CH2 CH2 3, -OH,
CH3
D -o~ -S-CH2-CH2-OH ~ s c ~ ~
-S-CH2-COOH' -S ~ No2 ~ -O ~ -S3H ' -NH2,
N2 ~ H3
-NH-CH3, -NHC2H5, -NHC3~7, -NH-CH
~13
-NH-CH2-CH2-OH, NH-CH2-CH2-OSO3H, -NH-cH2-cH2-o-cH3,
~ CH2-CH2~
-~H-CH2 CH2~ -NH-CH2-CH2-S03H, -NH-CH2-COOH,
CH2-CH2
-NHCH2 / CH2-CH ~ / CH3 / C2 5
¦ -N O , -N \ , -N ~
CH2COOH, \ CH2-CH2 C~3 C2H5
C
.:
H3lC CH3
N ~ -N ~ , -NH ~ , 1 CH2 CH2 SO3H
ICH2
SO3H
. SO3H
~NH ~ COOH -NH ~ ~SO3H , -NH
SO3H
OH
-NH ~ 3 ~NH ~ - COOH , -NH-OH , _NH_NH2
SO3H
-NH-NH ~ , _NH_CH2 ~ -NH-CH2-CH2 ~ ,
NH ~ 503H -NH ~
SO3H
,
:,
.
.
,
' ' ' '
6~
Preferably, the radical Y in the formula denotes a chlorine~
bromine or fluorine atom or a sulfo, amino, me-thyl-amino, dimethylamino,
~-hydroxyethyl-amino, ~-methoxyethylamino, ~-sulfatoethyl-amino, ~-sulfo-
ethyl-amino, N-methyl-N-~ -sulfoethyl-amino, carboxymethyl-amino, N-~-
carboxyethylamino, N-(carboxyphenyl)-amino, N-(sulfophenyl)-amino, N-
(disulfo-phenyl)-amino, N-(sulfonaphthyl(l))-amino, N-methylanilino, mor-
pholino, isopropoxy, phenoxy or ~-hydroxyethylthioether group.
Further compounds of the formula (1) which should be mentioned as
being preferred are those in which D is a benzene nucleus and R1, R2,
Kl, K2, Y and X have one of the above mentioned meanings, especially the
preferred meanings, and also compounds of the formula (1) in which D de-
notes a naphthalene nucleus which is bonded in the 2-position to the-azo
group, Rl represents a hydrogen atom and R2 represents the sulfo group in
the 6-position of the naphthalene nucleus, or Rl is sulfo and R2 is hydrogen,
and Kl, K2, Y and X have one of the above mentioned meanings, especially the
preferred meanings.
Further compounds which are particularly preferred are those of
the formula (1) in which D represents a benzene nucleus, in which the group
-S02-X is in the meta-position or para-position relative to the azo group,
or in which D denotes a naphthalene nucleus which is bonded in the 2-posi-
tion to the azo group and which contains the group -S02-X in the 6-position
or 8-position, and Rl, R2, K , K2, Y and X have one of the above mentioned
meanings, especially the preferred meanings.
The aromatic amines of theformula (2) are known, for example from
German Patent Specifications 1,278,041, 1,276,842, 1,150,163, 1,126,542 and
1,153,029, from German Offenlegungsschriften 2,154,943, 2,100,080, 2,o49,664,
2,142,728, 2,034,591 and 1,943,904 or from German Auslegeschrift 1,204,666.
Aromatic amines of the formula (2) which may be mentioned are, in
':
particu]ar, the fol:l.owing compounds: aniline-3-~-su:Lfatoethylsulfone,
ani]ine-4-~sulfatoethylsulfone, 2-amino-toluene-4-~-sulfatoethylsulfone,
2-aminoanisole-4-~sul.fatoethylsulfone, 2-amino-anisole-5-~suLratoe-thyl-
sulforle, 2-amino-4-~-suLfatoethylsulfonyl-benzoic acid, 2-methoxy-5-methyl-
aniline-4-~ suLfatoethylsulfone, 2,5-dimethoxy-aniline-4-~-sulfatoethyl-
sulfone, 2,4-dimethoxyaniline-5-~-sulfatoethylsulfone, 4-aminoanisole-2-~-
su~LfatoethylsfuLfoneg 4-aminotoluene-2-~-sulfatoethylsulfone, 4-~ sulfato-
ethylsuLfonyl-aniline-2-su~Lfonic acid, 5-~ sulfatoethylsulfonyl-aniline-2-
sulfonic acid, 2-chLoroaniline-4-~- sulfatoethylsulfone, 2-chloroaniline-5-
B-sulfatoethylsulfone, 2-bromoaniline-1~-sulfatoethylsulfone, 2,6-dichloro-
aniline-4-B-sulfatoethylsulfone, 2,6-dimethyl-aniline-4-~- sulfatoethyl-
sulfone, 2,6-dimethyl-aniline-3 ~-sulfatoethylsulfone, 2-amino-phenol-4 -~-
sulfatoethylsulfone, 2-amino-phenol-5~- sulfatoethylsulfone, 6-bromo-2-
amino-phenol-4-~-sulfatoethylsulfone, 6-chloro-2-amino-phenol-4-B-sulfato-
ethylsulfone, 6-nitro-2-amino-phenol-4-~ sulfatoethylsulfone, 4-methyl-2-
amino-phenol-5-B-sulfatoethylsulfone, 2-naphthylamine-5-~ sulfatoethylsul-
fone, 2-naphthylamine-8-~-su~Lfatoethylsulfone, 8-~ sulfatoethylsulfonyl-2-
amino-naphthalene-6-su~Lfonic acid, 6-~-sulfatoethylsulfonyl-2-amino-
naphthalene 1-sulfonic acid, 2-naphthylamine-6-~-sulfatoethylsulfone and
the corresponding vinylsulLfonyl~ B-thiosulfatoethylsulfonyl and ~-chloro-
ethylsulfonyl compounds.
The coupling components of the formula (3) are also known and are
described, for example, in ~erman Patent Specifica-tion 436,179. Coupling
components of theformula (3) which can be used are, for example:
C
) ~ ~ S03H
H03S 3 ~
H03S S03H
Y OH
N ~ N ~ ~ ' ~
~ ~ 3 / 503H ~ ~ rL
S03H H03S S03H
HO y OH Y OH
N ~ N ~ N ~ N
~ ~ ~ N ~ ~ ~ ~ H ~
HO S NH NH SO H OH NH 3
3 3 ~ S03H
H03S S03H
OH y
WH
H03S/ 103H
1) -10-
I OH
D HO S ~ H035 ~
OH SO3H
" ~ NH ~ NH ~ S03H
H03S 3
N ~ N OH
~ HO3S ~ S031~
S03H
N ~ N
HO S~ 03H HO S ~ 503H
Y OH
HO35 ~\NH 1N;~NH ~SO H
' ~' ' ' :
,. ` .., ~, . ' ' ' '
~h~
HO3S I NH N NH ~ SO3H NH 1 N
SO3H SO3H
OH Y OH
HO S / ~ NH N WH ~ 3 53H
SO3H
y
N ~ N
/ ~ ~ OH Y
HO NH NH \ ~ N N OH
3H ~ ~ 3 3
~ H SO3H
N N ~
/~N ~ J`~
HO NH NH SO3H
3 ~ 3
y S 3
)`N~ HO NH ~N HN OH
H S/~ NH OH HO3~,~ o3H
SO3H SO3H
D -12-
in which Y has one of the above mentioned meanings.
The diazotization of the aromatic amines of the formula (2) is carr-
ied out by generally known methods. However, care must be taken that these
aromatic amines, and the diazonium salts obtained therefrom, are not subjected
to strongly alkaline conditions during processing.
The coupling of the diazotized amines with the coupling components of
the formula (3) is preferably carried out in a pH range between 3 and 7, at
temperatures between -5 and +30C.
If a hydroxy group is present in the o-position relative to the azo
bridges in the radicals of the diazo components, that is to say if Rl = OH in
the formula (1), the dyestuffs are converted to the heavy metal complex dye-
stuffs by adding a heavy metal donor to the dyestuff solution or the dyestuff
suspension, if necessary with an acid-binding agent and if necessary by treat-
ment at elevated temperature (in general the reaction can be carried out at
0 - 120C) until the conversion to the desired heavy metal complex dyestuff is
complete.
Examples of heavy metal donors which can be used are: copper salts,
such as copper sulfate, copper chloride, copper acetate or copper carbonate,
chromium salts, such as chromium formate, chromium acetate, chromium sulfate,
potash/chrome alum or chromium/salicyclic acid, or cobalt salts, such as cobalt
sulfateS cobalt chloride or a cobalt/tartaric acid complex.
Acid-binding agents used when converting the dyestuffs to the heavy
metal complex dyestuffs are preferably alkali metal salts of weak inorganic or
organic acids, such as sodium carbonate, sodium bicarbonate or sodium acetate~
If Rl in formula (1) is an alkoxy group, preferably a methoxy group,
this can be converted by known methods~ during the reaction to convert the dye-
stuff to the heavy metal complex dyestuff, preferably the copper complex dye-
stuff, to a hydroxy group and the latter can participate in the formation of
- 13 -
C
the complex.
If Rl in formula (1) is a hydrogen atom, this can be replaced by ahydroxy group under the conditions of oxidative coppering [Angew. Chem. 70,
232-238 (1958)], with simultaneous incorporation of the said hydroxy group into
the complex compound. The oxidizing agents used are advantageously derivatives
of hydrogen peroxide, such as sodium peroxide, salts of peroxysulfuric acid or
salts of perboric acid, but preferably hydrogen peroxide itself. Advantageous
reaction conditions in general lie at 20 - 100C and pH values between 7 and 3.
The starting dyestuffs of the formulae ~4) and (5) can be manufac-
tured by known methods, for example by the processes described in GermanAuslegeschrift 1,126,542.
The resulting dyestuffs of the formula ~1) or their heavy metal com-
plex compounds are separated off by generally known methods either by precipit-
ating from the reaction medium by means of electrolytes, such as, for example,
sodium chloride or potassium chloride, or by evaporating the reaction solution,
for example by spray-drying. If the latter method of isolating the dyestuff is
chosen, it is advisable, before evaporating, to remove any amounts of sulfate
which may be present in the solution by precipitating these as gypsum and
separating them off by filtration. In some cases, it can also be desirable to
supply the dyestuff solution direct, if appropriate after adding buffer sub-
stances, as a liquid preparation for use in dyeing.
The present invention also relates to the dyeing and printing of
cellulose and polyamide fiber materials with the dyestuffs according to the
invention.
Cellulose fiber materials are understood as meaning preferably cotton
and regenerated cellulose, but also other vegetable fibers, such as linen,
hemp and jute. Polyamide fibers are to ke undexstood as meaning both those
- 14 -
of natural origin and those of synthetic origin, that is to say both wool and
other animal hairs and silk and also polyamide 6,6,polyamide 6, polyamide 11
or polyamide 4.
The dyestuffs according to the invention can be applied to the said
substrates by the application techniques known for reactive dyestuffs. They
are distinguished by clear shades and high tinctorial strength.
Thus, with these dyestuffs very good color yields are ob-tained on
cellulose fibers by the exhaustion method from a long liquor, using very di-
verse alkali addi-tives.
Excellent color yields are also obtained on cellulose fibers by the
pad method, and the dyes can be fixed by a residence time at room temperature,
by steaming or with dry heat. ~on-fixed portions of the dyestuff can be
washed out easily.
Intense prints with outlines in a good state and a clear white
ground are also obtained by the conventional printing processes for cellulose
fibers - in a single phase in the presence of sodium bicarbonate or other
acid-binding agents in the printing paste with subsequent steaming at 101 -
103C or in two phases, printing with a neutral or weakly acid printing paste
and then either passing through a hot electrolyte-containing alkaline bath or
over-padding with an alkaline electrolyte-containing padding liquor and then
developing by means of a residence time, steaming or dry heat. The appearance
of the prints is only slightly dependent on changing fixing conditions.
The dyeings on polyamide fibers are usually carried out from an
acid medium. Thus, for example, acetic acid or acetic acid and ammonium
acetate an be added to the dyebath in order to obtain the desired pH value.
In order to obtain a uaable levelness of the dyeings, it is advisable to add
conventional levelling agents, for example those based on a reaction product
of cyanuric chloride with three times the molar amount of an aminobenzene-
- 15 -
' C
sulfon:ic acid and/or of an aminonaphthalenesulfonic acid and/or those based on
a reaction product of stearylamine with ethylene oxide. The dyeings can be
carried out either at the boil or at 110-120C.
With regard to the coloristic properties of the dyestuffs according
to the invention, it must be emphasized in particular that these dyestuffs are
distinguished by a very good uptake from a long liquor, by good color build-up
by the conventional dyeing and printing processes, by an identical depth of
shade when dyeing on cotton and regenerated cellulose fibers, by levelness of
the dyeings and prints produced therewith and also by a uniform appearance of
the dyeings from a long liquor in the presence of different amounts of electro-
lytes such as sodium sulfate or sodium chloride.
The fastness properties of the dyeings and prints obtained with the
aid of the dyestuffs according to the invention, especially those on cellulose
fibers, are appreciable. This equally applies in the case of the most import-
ant fastness to processing and in use. The fastness to light, the fastness to
wet processing, such as fastness to washing, fastness to milling, fastness to
water, fastness to seawater, fastness to cross-dyeing and fastness to perspira-
tion, and also the fastness to pleating, fastness to ironing and fastness to
rubbing should be mentioned in particular.
The Examples which follow serve to illustrate the invention. The
relationship between the parts by weight and parts by volume is the same as thatbetween kilogram and liter. The percentages are by weight unless otherwise
stated.
Example 1
281 parts by weight of aniline-4-~-sulfatoethylsulfone are suspended
in 1,400 parts by volume of water and 600 parts by weight of ice and dissolved
by adding 62.5 parts by weight of calcined sodium carbonate, whereupon a
pH value of 6.0-6.5 results. 205 parts by weight of aqueous 5N sodium
~ 16 -
f~
nitrite solution are then added, 10 parts by weight of kieselguhr are stirred
in and the solution is clarified. The filtrate is allowed to run at 0-5 C into
a mixture of 1,500 parts by weight of ice and 282 parts by weight of aqueous
31% strength hydrochloxic acid. The mixture is stirred for one hour at 0-5C,
the excess nitrous acid is then destroyed by means of amidosulfonic acid and
the pH of the resulting diazonium salt solution is then adjusted to 6.0 by
introducing about 45 parts by weight of sodium bicarbonate. This solution is
allowed to run, in the course of 15 minutes, into a solution of the secondary
condensation product of ~ mole of cyanuric chloride and ~ mole of l-amino-8-
naphthol-3,6-disulfonic acid and ~ mole of 2-amino-5-naphthol-7-sulfonic acid,
which is prepared as follows:
92.5 parts by weight of cyanuric chloride are dissolved in 300 parts
by volume of acetone and the solution is then allowed to run into 2,500 parts
by volume of water, with good stirring. A solution of 159.5 parts by weight of 1-
amino-8-naphthol-3,6-disulfonic acid and 60.5 parts by weight of aqueous 33%
strength sodium hydroxide solution in 700 parts by volume of water is then
added at about 20C and the mixture is stirred for 10 minutes, after which a
solution of 119.5 parts by weight of 2-amino-5-naphthol-7-sulfonic acid, 46
parts by weight of aqueous 33% strength sodium hydroxide solution and 150 parts
by weight of crystalline sodium acetate in 1,000 parts by volume of water is
added and the resulting mixture is stirred for a further 1 hour. After the
diazonium salt solution and the solution of the coupling component have been
combined, the mixture is stirred at about 20C for several hours, the pH value
being kept at 5.5 - 6.0 by adding a total of about 161 parts by weight of
sodium bicarbonate in portions. After the coupling reaction has ended, the dye-
stuff solution is clarified and the dyestuff is then precipitated by adding
about 4,000 parts by weight of potassium chloride. After cooling to 8-10C,
the dyestuff is filtered off and
- 17 -
C
dried in vacllo at 60C. This gives a red powder which dyes co-tton in fast
red shades in the presence of acid-binding agents. The dyestuff has the
following constitution:
C1 OH
N ~ ~ ~ 21 2
HO NH~J\N}I ~so3H CH
CH2 CH2 02S ~N===N ~ 1SO3H
OS03H H03S SO3H
Example 2
251 parts by weight of 2-naphthylamine-8-~-hydroxyethylsulfone are
introduced in the course of 20 minutes into 660 parts by volume of 20%
strength oleum, the -temperature rising to 60 C. The mixture is kept at 65-
70C for 4 hours and is then allowed to cool to 30C and is added to a mix-
ture of 2,500 parts by weight of ice and 1,000 parts by volume of water. The
diazotization reaction is then carried out at 0-5C by adding 200 parts by
~rolume of aqueous 5N sodium nitrite solution, the reaction mixture is stirred
for a further 1 hour at 0-5C and the pH is then adjusted to 5.0 by adding
1,184 parts by weight of calcium carbonate.
This suspension is added in the course of a few minutes to a solu-
tion of the tertiary condensation product of 1/2 mole of cyanuric chloride,
1 mole of 2-amino-5-naphthol-7-sulfonic acid and 1/2 mole of aniline-3-sul-
fonic acid, which has been prepared as follows:
92.5 parts by weight of cyanuric chloride are dissolved in 300
parts by volume of acetone and the solution is then poured into 2,500 parts
by volume of water, with good stirring. A solution of 119.5 parts by weight
of 2-amino~5-napthol-7-sulfonic acid and 45 parts by weight of aqueous 33%
strength sodium hydroxide solution in 1,000 parts by volume of water is then
added at about 20 C and the mixture is stirred for 10 minutes, after which a
- 18 -
C
further solution of 113.5 parts by weight of 2-amino-5-naphthol-7-sulEonic
acid and 45 parts by weight of aqueous 33% strength sodium hydroxide solution
in 1,000 parts by volume of water is added and 150 parts by weight of crys-
talline sodium acetate are then sprinkled in. 86 parts by weight of aniline-
3-sulfonic acid are then added and the mixture is heated to 90-95C, the pH
value being kept at pH 6.5 - 7.0 by adding sodium bicarbonate. The mixture
is stirred for several hours at the said temperature and at pH 6.5 - 7.0 and
is then allowed to cool to room temperature.
After the diazonium solution and the solution of the coupling com-
ponent have been combined, the mixture is stirred for several hours at about
20C, the pH value being kept at 5.3 - 6.2 adding a total of about 64
parts by weight of sodium bicarbonate in portions. After the coupling reac-
tion has ended, the mixture is warmed to 60 - 65, the gypsum whichhas ~re-
cipitated is filtered off and washed with hot water and the filtrate is spray-
dried. This gives a red-brown dyestuff powder with which violet dyeings and
prints can be obtained on cellulose fiber materials in the presence of acid-
binding agents. The dyestuff has the following constitution:
C 2 3 ~ SO3H CH2-OSO3H
52 HO NH OH S2
~ N=== ~ ~ ~ ~ N===N ~ ~ ~
HO3 ~ 3 ll 1`N ~ HN ~ ~ SO3H ~ SO3H
In a manner analogous to that described in Examples l and 2, dye-
stuffs can be obtained from the diazo components and coupling components
listed in the table which follows: these dyestuffs dye and print cotton in
the indicated color shades.
- 19 -
~ I ~d
c~ C ~ a~ ,c a) a) a) a~
.C o u~ h u2 h rd ~rd h h h
u~ +~ a~ hh C ~ ~ ~ ~ ,C r~
,~ o h O (V O a) u~ C) u~ C)
O c~ ~I bD ~I hO ~ 0 h
O C ~1 ,&~ ~1 ,C ~ ,C~ R t~ ~ ~C
V O ~ ~ ~ ~ ,~ ~ ,Q +~O ,Q +~
+' ~ O
c a) o ;~
& ~1
o o a~
O tQ N ~
O ~1 ~3-rl rl
q~ C~
q~ O ~d
&' O ~D ~
r~ 1, 0~ ~
O O O ~ ~I r~ _ = _ _ _ _ _ - _
.
~ p~ C I
C
+~ h co rl O
~ ~ O ~ +~
(I) ~ P~
-&
O q~ O I
O ~1 ~1 co
O O O ~
+~
,~ ?
+' ~ +~ C
(1~ , +~ o u~
~ $ +~ ~ o~ :rL ~n cn ,i ,
O ~ Q h
~1 q l q-, o ou~ ~t IA ~ rl,S:~
O ~ ~ ,C ~ I I I ,C,1~
t.l I I I Y ~1 0 0 C)
O cn cnC~ c~ o
N I ~-~rl ~-1 ,C I O
td ~ ~ ~) ~t ~ C C O
O +O ~ a~ XO
h ~ C ~ O ,5~
~ N R N ~ N ~ N ~ N
4~ o ~ 4~ q~ o q I oq, o ~~ +~
O O O ~,~ O O q~ q~ ~1 +'
a~ & ~ &~ ~ aJ & ~ +~
O q~ 0 4~ ~0 ~ ~0 q~ ~0 ~0 ~ ~0 ~ ~ "
~ ,Cj ~,C
N U~ N ui N a) N ~ N N C) N a) N O N 11~ N ~t
H a~
lÇi o ~ ~ L~ ~0 ~ cO CJ~ O ~ N
~;
-- 20 --
a~ a) ~
~ s~ ~
.c: O
U~ ~ U~
O c) ~1
O ~ ,D ~ 5~ h 5~ h ,~
o
~rl ~
q~ ~ R
o
a~
~1 ~ r~ I
O ~0 ~o ~ o
o~ 4~
cl O ~ O n3
b~ +' ~ ~1 ~
c~ ~ co
~rl
O ~ ~ R - _ - - - - ~ _ _ _
::~
o ~ h~o
V
O S 1
~d o ~ ~0 c~
U7 ~rl ~ rl
R S~ ~ a) R
R ~ o
R ~ R ~ ~1
v ~co ~ ~
I ~ ~ r
~ O O
R c~ ~ CQ CQ
a) C~ ~ u\ I R ~rl ,1
R I cu ~1 ~1 1 1 ~ ~rl ~ ~
~1 ~ ~ 3 R R a~ ~rl R R R
~3 O R ~ +~ R
o U2 ~ a) ~ ~ rd ~ ~1 ~rl ~ ~1 ~1
C~ ~ O~i~ O~
O
R ~ O o ~ ~ R ~ ~ R
~,~ ~ o R ~ rl o O O O ~1 o ~rl o ~rl o ~rl o
R I o ~ O ~ o, ~ ~ q~
CQ 4r CQ q~ 0 ,~ ~D ~ R O
I r~ r q~ ~ rl I r~ ~ u2 I ~r
_~ r 1 _~ r1 ~ ~ CU r-/ ~\J rl C\l r 1 t:\l r l C~l r~ l r-l C~l r-l
~H ~ ~ U2 4 1 I G I I G~l ~ H ,~ C~ H U2
O ~ O r~ O Cy O C~.l O ~ O +~O ~ O ~ O I~ O ~ O r~
u~ o u~ o u~ o Ul O U~ OU~ O V~ O 11
r~ id r-l C~ r~ ~rl r~ ~rI rl ~d r-l ~d r I ~ rl ~d r1 c~ r-I ~ r1 ~
~0 ~ ~ ~0 r-l ~O r~ O ~~O ~ ~O ~ ~O ~ ~O ~ O~ O
rJ
~ r~l r-l r-l r-l r-l cro~ r-l C\J r-l (~
3~ o
æ
-- 21 --
,
~6~9
a
n~ ~ a~a) ~ a
o
,C ~ ~ ~d
O u~
O U bOrl ~D~ bD
O ~ ~1
o ~ ~ ~ ~ ~ ~
I ,,
o ~ ~ ~ o
u ~ ~ ~ U Ei ~ ~h U
bO q~ 0 ~ O ~
O ~O O ~ U
O O o ,~ 'h .~ ~
o - ~ U
O U ~ ~ ~ O
'~ '~ CO ~ C
~ ~ O ~ 0
a) ~-~ u ~ r~ U
U ~ '3 ~ U ~
o ~ I o I o 4~ 1~ o I
O ~1 ~ CO ~ O ~1 ~ L
I I r I I 1 ~ ~ ~
I ~o ~ o ~1 ~ I ~ O
~o ,~ r ~ ~ 5
~ ~ ~ o
O R ~ ,~
~ ~ ~ O U~
C) ~ o
~ ~ O
N1:~ ~ O O ~ q~
~d~3 r~ r1 ~ rl ri ~ r~ (L) r1
i~R ~ rl ~ ~rl r~ O
~1 r~ CO~ ~rl~0 ~ C) ~ ~l ~ Il) I rl C\l I
I ~ 0 tl~ ~H O ~H ~ ~H
O 1~ O IO I O q-l ~I rl O ~H O q~ O
r~ U r~ U r ~ O ~ rl O ~ I
~3 r~O Or~ O O rl ~I r~ ~ ri r~ r I r~ cd r~
~0 q-l ~o 1 4~ ~o ~ o o ~o ,~ ~o ~o ~ ~o r1
r~
,~ O ~ CO O~ O r~ C\J
-- 22 --
., ~ `.~
. ~
a~
~ o s~
~ ~o
O ~ ~
O ~: ~ H ~) ~ ~1 ~rl ~)
~ O ~1 ,0 ~ ,5~ ~ S~ 5-1 ,n +~ Sl
g
q~ Lr~ ~ O ~ I
+~ ~ O ~ O I ~r~ O
R ~ O ~ ~:
O O Lq ~
O ~h ~ I O ~ ~H ~1 I C`J ~rl O ~ I O
^ ^ a) c ~ H ~d ~1 ~ ^ ~rl
~H ~ H rl ~ O ~-H r-l (L)~H I ~ rl I C)
r1 O O ~ rl g ~f ,5 r~ ~ ~ O ~ ,5~
O ,~ ri ~ 4 h ~ O ~H
~, ~ q r~ O ~ ~
~rl ~rl I ~ ri ~rl ~rl I ~ ~ ~J ~rl C~ I O rl ~d
CO ~rH O 4~ h CO ~rl I ~ +~ CO ~ rl
~ ~ I ~ rl
Lq ~ o ~ ~ ~q ~ o ~d o 4-, Lq ~rl O ~ I ~
Ll~ ~ ~r C~ rl O +~ rl ^ I ~
r~ ~r~ ~q ~ c~ ~ ~rl ~ ,q ~ r I ~
o ~ 7 o I o ~H I o ~ o o ~ ~ c~ s ~ ~
V O rl ~1 11~ V O rl ~1 ~ ~ ~) C) r~ ~ ~ O
1~ .
I ~ , ~q ~ ~ ~
~ r,~ r~ O O I r~ O
r~ Lq s Lq ~ q I
~ ~ ~ ~r
d ~ Lq r~ ~ d tlq
~) O F O r~ O I ~1 Lq o r-l
S~ ~ O +~ r~ I ~rl-L~ ~ I
O +~ ~H ~q ,s} ~3 1 ~ ~ tl3 ~ ~
- ~ r~ rH~ ~ t~ I O rl ;~ ~D
O ~rl Lq ~ R
t~ ~ r~ ~q ~ Lq r~ ~rl ~rl ~L) Lq ~ ~r
O 1~ r rl ~ O c~ ~ ~rl
~d ~ CO ~1 rl ~O ~ ~ a) C\J r-l
~r ~H +~ tH ~d ~ tr l ~( ~H O tH cqq~ H O
O td O O ~ O ~H O r~ O ~rl O ~H
~q tq C~ ~rl Lq O r~ ~q ~Lq c~l ~d r~
r ~ Lq ~ Ia) Lq
r~ Lq r~ r1 0 rl ~r r1 rl r~ a~ rl r1 ~J rl r~
~0 1 ~ ~t~ ~ ~ rd ~ ~ ~d
N ~ C~.l t~-r Lq C~ l L~C~J C~ 1 tH ~ C~
rl
u~ ~O ~ co
X O
~i
-- 23 --
,
o
i~
~l o
r ~ r~
o ~ o a,) o o a)
O h h h h h h
I 1- ~r~ I ~rl ~) ~ L~
r4 1 ^ I r~ > r~ r~ ~ rO ~Q 1 r-l
O (r~ C~l O (~ rl O ~ CU O O
+~ ~ r~ r~ r~ I C ) ~ rl
S:r1 ~ O O R ~rlr~ ,~ O O S I ~ ri ~ O O ,C ~ r~ ~0
s:+~ ~ O ~ +~ ~ o ~ O ~ ~ ~ I r~ )
Oq~ ~rl ~ ~ 0q I ~rl ~ ~ r~r~ (~) C\l r
P~O ~ ~ r-l r I ~0 ~2 ~ r~ r~ ,~ O ~ ~ r I r ~ I O 1~ f
8P~ ~o r ~ r~ r
t,t~ ~ a I ~ rl t~
O O 0 I rd h C ~ ~ rJ~ h cO I ~ ~ $o ;~ rO O +~
r-l~ ~ rl ~ r~ ~ r~ o r~ ~ r~ o r~ l h~ ,5
~1c.) r~ o ~ ~c) rl cJ ~) q~ c) rl u +~ r~
~ c3 ~ O S~ O ~ CO ~n o
O O C) ~ ~1 0 C) n~ ~ O t~ ~ ~ O ~
+~ i r I rl ~ +~ ri ~rl ~ r I +) 5~ r~ r~ r ~rl ~o r~
a3 ~ I o ~ O ~d ~s rl c) r-
a) ~ r-l o ~ ~ r-l o r-l (L) ~ r-l o r I ~J I o
r R r ~ c) r-l rl
O ~1 O ~ J O q-l O ~rl ~ R 8 q I O ~rl ,~1 R O q-l ~r O r,d O
V O ~ r~ r,d rd V O ~ rcl rd r,d V O e. ~ r,B r,r~ V O O
r~
;3~ O -~
a) ~r ~
O ri ~) O O
~ rn h r~J ~ $
rH rH r~r r,d
r~
I I I I 1: rp
R rn c~ rn ~n rn
O
R R R R R
r~ rr~ ''I rrlr~ r l ~rr~
~rl ~rf ~rl~rl ~ rl
~0 rd r,d a)r,d rd a) rd O ~ Q
rd ~ O~Hrrl o r~r 8 q~ 8
1~ O O q~oO t~ o rH o q-r
rn a) r~ r~rn a) rn r~ tn r~ rn r~
O R O rna~ rn a) rn ~ rn
r-l O rl r~¦r-l O r-l ~I r-l r~l r-l r-l
0 4~ 0 ~ 0 4~ 0 ~ O 1~ 0 ~
~ r~ r~
C~ rn C~ aJ ~ rn
a~
O r~ l (r) ~ L~
. ~ ~t ~ ,:J
~3 ~o
-- 211 --
r~
~ ~.
r
r,~ ~ C~
O
+'
i~ O rn
O ~: ~ ~ r
V O
q~
a~
r o~ ~ ~0 El r ~ ~ ~0 r,~
e
I ~ ~ ,I rn ~ ~ ~ I El ~ r.
r~ . ~ ~ ~ ~ r
q~ ~ rY~ C~l r.~1 C\J r.~ ~ C~l c~ ~
O O r,~ O r,~ ~o O ~ I
~ +~ ~ O O r~ O ~ O rl a~ ~ a) ~ o ~1
O U ~ ,5i ~ ~ O rd I ~ R u rd ~ s~
u ~ S~ X ~ ~ ~~d ~ o ~ ~r r-l rd ~ X r-l ~r $
bO O O Pl 0 r1 ~O O q O r1 0 0 0 Pl O ~ P r
S~ ~I r.~ r~ 5 q ~ ~ 5
r u ~ rl ~ ~ u l~r r~ u I rI 1 ~1
R CO C-- I R l;d ~ O ~ cO ~ ai
O U I ~ I ~ O U q ~ 1 ~ O C~
VO ~ rl r~ .d rO ~r~ ~ CO ~rl O q~~ ,rl ~rl 0 4
r~ ~ ~,1 U ~ O~ ~ I U ,s:: O r,~ O
. rn ~ ~ r,~ ~ ~n ~ O r,~ +q~ rn, r~ ~ C~ +q) O
a~ u ~ ~ ~ :~, I u ~ ~
O~ U ~1 ~rf r.~ O ~ U ~ ~rl r.~ O
~ R ~~ r,~ ~ ,q ~3
O tH to tO I ~ V O rl tH 11~ ~1 o tO tH O
O I O
~u ~1 ' ~ 'q
tH ~ I O ~
r~ O tH _ O
r~n ,-1 :., tH rd ~
O ~ 1~tH t ~ tH
U ra
0~ ~I r
,q OI ~ I I rl
~3 I ~ o~? g
U) ~ ~HO +~ IU O O q a~
o ~ I ,~ rd Rq ~ O
f3~ '~ I rn ~ tH
u r~ ,qI r~n
~ O C\l ~C\l I ~ C~l ~I c
O ~1 0 4 1 ~rH q~ q I O 41 ~H
O q~ O O O ~:t 0 4~ 0 0 ~ O tH
rn ~ rn ~rn I ta ~ rn u~ o rn :~
a) rn ~) ~H
~, '0~ 1~o ~, ~0~0 ~rH ~0
~,~ q rn
C~ a) C~ C\~ ~ C\l O C~l c~ rn C\l a~
~ ~o ~ coo~ o~ c\J
rd ~ ~ ~ ~~ ~ u~
X O
F'l ~i
-- 25 --
r~
~. .....
a)
~ R aJ
'U~
~ .C
o ~o)
~1 r~ R ~1
O C a) a) ~l~rl' a~ a) a~
o 5
l l
q~ C~ o q~ C~ o q~
O~r~ C O ~r c I ~ O
o o o X a) o o c ~ '~ ~ '
,~ ~,1 o tn o o ,1 ~ Q ~rl
o ~ 3 o o a) ,1 ~ o o ~ R ~ Co 0 ~1 ~ ~ ~
,oJ ::~ ,CI ~ o U~ R ~ R O
R ~1 ~3 ~rt Ir\ ,1 ~1 ~; ~rl co ,1 ~1 ~0
R q~ 0 ~ ~ o ~ ~ C ~ ~ ~
O o~D R ~C O ~D R O ~ .C o ~) c~
O ~ ~ rd ~ R3 ~ ~ rd O d ,C c) o ~ ~C- I O
C) ~ r~ I R R ~ ,~ 1 C
rd O o c~J ~3 t3 rd O O C~ ~ - rd 5~ ,C ,~ R v3 : rd a) O r-l R C~l
R o d C ~ ~ I o d C ~ o o ~ ~o ~ q~ o d rC 0~ 0 1
~i ,QI h C O ~ h rC O ~rl ~I rC ~ I rC --I R
R ~ ~ c~ O rC R r1 ~rl R C~ o '~ ~ I C ~ ~~
O ~H c) I O v ~ ~rl C) I O u ~1 ~ i-l O rd ~D ~H c~ I ~d ~ C
v ~ t) I C q~ R ~d ~ R , I ~ ~ col , I ~d
Lq ~rt O ~1 0 rl Lq rl O r~l O ~ Lq R ~ ~d O Lq ~rl O ~3 0 q~
R h R q r ~ R h R q~ r-l R ~ C o ,C 5 ~ R C o
d R El rd ~ I d R ~ rd ~ . d t~ ,1 C O d R ~ C ~ rd
R ~ ~ ~rl Lq 3 R ~ H Lq +~ R R P~ ~ R ~3 tp R ~ rl ~r~
o ~ 1, C) II o ~ I c,) I a) o q~ 4~ o ~ o ~ I o ~d O
~) ~.) rl 1~ t l r~ O 0 41 R ,~ ~r R
C
O O I R O r-l ~H
r
~H ,~ r~ ~H Lq
u Lq ~ C
RLq Lq ~, Lq ~ R
C~ , L~ C r ~
O~ ~ ~ ~ ~ ~ ~t
OR R ~C ~ R R R
N'~R ''R ~J Lq R rl~ R ~1
rq-l ~H q~ I ~H g ~r Lq ~1
O O O ~ O ~H O ~ O
Lq 11) Lq IL) Lq (~ C Lq
O R QJ R a) R ~ Lq ~ +~ 3)
O q-l o ~H O r~l O ~ O, O
~ R
C\.l U~ q ~ H C~.l
rl
D ~ CO
~c æ
-- 26 --
~'
~'
rd l rd
0 ~ ~ a~
~rl
~, o o a)
O c~ r~ ~D
O S I rd rd ~d rd ~1 ~ ~d rd
V O ~ h S-
I q~ c~'o q~
I O O q ~ O
3)~1 ~ rl ~ O O ,~ a~ o
r~ O
0~ ~ ~rl I ~0 C~ ~ ~13 0 ~; qO
+~ r I I C\l rd O U2 1 a.) o ~ o
r1 ~ ~ crl r~ d c 10 rO ~ ~ ~rl
q~ O ~ q "~ I o ~ rl ~j
O 0 0 1 0 ~O ~ O -d 0
~ ~ c rd ~ rl r~ ~> s l ~o c\l --d
O C~ --d ~ O 5:1 CJ 0 1 0 rd C~ 0 ~ rl
.) ,~rl ~ ~1 ~ ~ q-l C~
-d $~ ,~ q ~ -d O O C~J 0 ~ -d C) I 0 0
O O ~ r l ~ O rd ,~ rl _ O rd rO ~
~rl ~ d u~ ~ O rl ~ ,5:1 r-l ~rl
co 0~ r~ 0 C~ ~ ~ ;~j ~
O C~ I I O ~ ~ rl O ,~
O rl ~rl O rd r1 ~rl C~ I O C~ O ~rl C~ 0 ri -.
V ~ ~ R ~rl ~ ~ CO ~ ~r ~ R~ d ;~
U~ R ~ rl O rl O ~ u~ ~rl CO R
~ c~ ~ R h~ ,R ~ ~ rDo R ~ I 0
--d C~ r1 ~ d R ~ rd ~ R rd R R rd
R R R R t~ 0 ~rl U~ rl R 0 ~ rl O
v o o ql co V C~ I ~? ~o ~ O ~ ~ C?,
1 1~ 1
I 1? O O O I I R
~L o ~ ~ ~ cn ,~ O
~ o ~ ,R r1
R r1 C) U~ U2 U2r1 ~ r
~ rl I ~
O R ~ ~ R ~ o
1:~ O ~) C? ~? ~
O R R R R R R
C~ 0 0 rl ~ rl ~10 g ~j
O I q~ R 0 Q~ 0 ~) 0 a) C\J r1 CU I
~rl q~ q~ 0 4~ 0 q~ O
O r1 O O ~1 0 q-l O q~ O r-l O ~
~I? +~ a) R (I~ ~ ~ R
r-l a? r-l O 1
O O O q~ O ~ O ~ O ~O O O ~
0 ~ R
(U 4~ C\l a) N ~OJ ~? C`
a~
O~ O ~ C~l ~ ~ Lf~
~j O U\ ~o ~o ~o ~o~o ~o
æ
-- 27 --
f~
r`~3~3
~>
~d ~ ~ ,S ~ h
O h L/) h I o
u~ ~ ~ ~ 3 ~ a) ~ v
~ o u, C) o ~ ~a b4 ~1 ~
O t~ ~ rl ~4 ~I t)4 ~ ~ ~ ~0
O S: ~ 3 ~1 ~.> ~ C ~ h h C~
O h ~ ~ h ~ :~ ~' h O O h
I I ~
~,s
Orl ~ O O O ~ O C~
Q) O O ~
4~ V
O ~ ~ U~ O ~ ~ O rl O a~ ~
~ o u~ O ~d ~ O O O
~ ~ I ~ ~1 ~ I ~ 3 ~i N
O O ~ ~d O I O ~ o o u~
O ~ ~ ~ N ~ ~-- ~ I~ ~) .
~ ~ O O t~ O ~ a~ o
1~ h ~rl ~ a~ U h O ~ ~ O ~ ,~
. ~1 Il~ h .S r-l ~ rl ~ h 4~ ~ .C ~ h rC
_I O ~ O ~: O O ~ O P.,
o ~ ~ ~ 2 g 3 a~ g ~ g ~: ~
O ~r~ V I ~1 ~ rl 4~
a~ td h Ei ~ U~ tli t) I
Ul rl O ~ Vl O ~ rl O
S~ h ~
~ ~ a
O
O ~ ~ ~ N 3 ~ N ~ I ~d
I ~
~ 2 ~ , g
.,, ~ ~ , o~ , o o
. u~ g u~ g
:~ ~ S ~ 3 U~R _I ul v~
~ o,o U~ I ,o , , o
~ ~ O ~ `D ~- ~1 11 ~1 1 1 ,~
g ~ ~ R ~ ~ ~ R
Pc Ei .~ --l R ~I R 0a~ o ~ ~ o
U~ R 4~ j~ R R
~ I ~ I ~ ~ ~ ~ Ei R
o ^ ~ I ~l ~ R RI 'n R
t~ N 11> 0~ dN ~I ~ > N ~1
~d ~ O ~ P.l ~ ~ ~ Ro ~ ~ ~ ~ g ~ R
a o n~ o Ro R O ~ OO ~ O ~ O ~1
v~ ou) O u), U)Vl O m
Q) ~ O RG.) R ~ u~
O, O Fl 0 ~3 0 ~ O 0 4-1 0 ~ O :~ O O
N ~ t~l N N N N ~ N N Ul N O N 0.~ N
~ I~ ~ O--I N t )
X O ~ ~ 'D `D ~I~ I~ 1-_
U~ Z
- 28 -
C
3f~
~,
, ~ ~ ,
O rC h .5::
/~ ~ 3 ~ U~ 3 ~ ~ ~
~ O O q~ o ~ bl)
O (~ ~ 1~
O ~: ~1 ~ ~ I 4
O :~ ~ ~ ~ O ~ h O O O
O
O ~ o 4~ ~o ~ a~
c~ a~ o a~ ,1 a~
_~ U ~1 ~ 6 ~
6 o ~o 6 ~ ~o e o :~ 6 ~ o L~o~
~1 6 4~ 6 ~ ~ 6 4
C ~ ~ S ~ 1 N 3 a~
O O U~ O ~ U~ u) 6 ~ Vl ~3 t)
O ~ td I C.) ,C I ~ t~S I V ~1 1
o r3 o ~ ~D O O ~ h ~ O S:~
h ~ ~ O ~ ,s~ ~ ~ ~
C O C~ ~ h ~ --ol ~ 4 6 :S
O O rC C O h 1:~ 0 .C ~ O
t~ w ~ ~ w ~
U) ~r~ O V) rl O U) rl O U~ 5 0 C
C h C C h C C h ~ cd C ~ C ~ .C
6 ~ ~ ~ 6 ~ ~ ~ Ei ~ ~ tJ 6,
C td C~ ~ rl C ~ td r~ ~ ~ ~ rl C n~
O N W C.~ O N ~ ~ O N ~d ~ O N w C
~ t~ C O
O I ~ rl O C) O
O ~
O ~ ~ ~ 'r~ rl w
~:: O I O I C~ 11~ O ~
a~ ~ ~ ~ ~1 1 1 ~ rS O I ~ O
P~ ~1 ~ O
O 00 ~ ~D rC W N ~ O 1~ 0
~t ~I w-- ~ w-- ~1 0 4~ ~ O ~ 41 0
C~ O ~ O ~ O ~1 0 d ~ ~1 ~ ~1
U) O U~ O V~
6 w~ ~3 ~i 6 ~ 6 -~ 6 1 6 ~ 6 C" 6
Ul Z
- 29 -
C
~ ,
a~
t~ ~ h ,~ r~
S O , o v) h v~ h
U) ~ 3 ~S 3
h O ~ 4 b4 0 ~ O
O O e ~ ~ F: e ~ ~0 ~ b4
e ~ ~ e
O g O h ~ O O h h ~ ~ ~ ~'
o ~ ~C~ ~ 4~
a~ o a~ o ~C ~ v ~ o
t~ I ~~ ~ O
O ~ rl L ~ O ~ ~ O a~ ~1 o a~
J~ ~ ~0 g O ~ ol o e ~ E~ ~0 g ~ -o~ o o
e
q~ O ~ ~H ~ 3 4~
o o v~ ov~ e td ~ o ~ o
~ ~ I I ~ e ~ ~
o ~ , e ~ ~ ~,
~ a~ o o e ~ c~ 0 ~ ~ O ~ a~ o o e
~: h ~ h ~ ~ S ~ ~ h
,~ ~ h ~ ~ ~ ~ h ~ O ~ rl ~ Sl h rC P~ h ~ _
,~ ~: ~ ~ a ~ e ~ ~ ~ g ~ e ~ P~
~ o~ e I o~ e~ x o~ e o~ e
O ~ I o ~ o
v) .~1 o ~ o ~ ~1 o ~ o u~ r/ O ~ O
~ > 3 rl 1~ e ~ h~
e ~3 ~ ,r: ~ e ~ ~ ~ ~ ~ e a ~ ~ e ~ ~ rc
e ~ o e ~ e
e ~ d s
. O O ~ ~ ~ ~ O O
1. ,1 e e e e ~ ~.
~d .C O O o o ~d
v, , v, v, u, v, v~
: o ~ ~ ~ ~ ~ o o
~ ~ ~ ~ rC rC
,.
e- ~a ~ o,~ o.,l o.,l o.,~ ~ ~
g
~ 4 a~ O ~ u
E; e e o
8 ~ ~ g u~ e ' o u~ g
o ~ e N ~ e ~ e
,, 4~ o 4~ ~ 4~ 1 ~ 1 4~ 1 ~ I ~ o ~ o
~ 0 4-1 0 0 N O N O N O N O q-l 0 4-1
~ e a~ e
. O ~O ~ O ~ O ~ O _10 ~1 0 ~ O ~
~ 3 e ~3~e~ e
N ON V~
a~ ~
~ ~ ~ u~ cn o
o 00 00 00 CO 00 00 00 C~
U~ Z
- 30 -
~ .
.
3~
a>
, ~ , ~ ~ ~,
~: O u) h Vl h h h h h h
h O O C~ O ~
O O ~ Ob ~I tlO rl b4 rl t~a h ~1 ~ rl bl) ,~ b4
O C
h h.D ~- .n ~ t~ ~ ~.
O O
O o ~ O
t~
0 2) ~ O ~ rl CO
I E3 ~1 ~: I ,
O O O O O O t~
rl ~ ~ ~r~
O O ~ ~ ~ O
S:4 ~ I I ~
~ ~ ~ ~1 0
a~ o o ~: ~ ~ o o
o ~ ~ o o ~ ~ V
P~ h ~ ~ -1 P, h ~
_I O P, O :~ O p, O I
g ~ ~:
O ~
o~
o ~ o v~-~ o ~ o
~: h ,C ~ h
O ~ I ~ cd O ~ I
:~ O I ~.
R
O ~ I O ~ O ~ V
4~ ~1 0 0 , I ~
. , ~ ~ o
~1 ~ ~ .C
I I u~ In ~O ~: 8, o,
a~ ~ ~ rC O ~ ~ ~ ~1 ~
g ~, ~ ~ t ~ ~ X o
C) a~ o o
V ~ ~ ~
,~ o ~ o
~ ~ ~ O
~1 4~ 1 ~ 0 4~ 0 ~ 0 41 ~ 4~
~ O t`l 0 4~ 0 ~H ~ ~ t 4~ ~ ~ ~
o ~ o :~ o ~ o ~ o o o ~ o l o ~ o ~ o o
~ ~ e ~
N ~d N O N a~ N a> N ~I N 1~N ':t N N N N N ~1
~I N t'') ~ L~ O a~ o
X Z
- 31 -
:
.5: 0 h h
V) ~ ~ ~ .C
h O u
O ~ ~ ~ ~
O ~ O O ~ C> ~ ~ ri ~1 ~1
O h h h h h ,D ~ ~ J--
0 ~1
~H~ ~ ~ O ~ ~ O
~> o ~ ~ o ~ ~> o ,C a~
o a~ ~1 ~ o ~> ~1 ~ O G~ ~ ~ O
O O I ~.1 0 0 0 1 ~ O O I
~ ~ ~ O ~ O ~ O
O o V~ ~ o V~ 1 o U)
; g o ~ g ~
~0 O ~ S ~ ~ O ~ S ~ ~ ~0 ~ S ~d
~: h ~ rl h h rl ~ rl ~ h ~rl ~ ~
,1 SL~ h S o ~ a~ ~ h ,S O ~ S ~ h S O O
~_t ~ C ~ ~ ~ `D C> ~ ~3' '
o S ~ ~ O S ~ E3 0 rC ~ ~1 0
O.rl O I O t~ rl V I O t~) rl t~ I O ~H
~00 e ~ ~0
V) ~rl O ~ O V~ ~1 0 ~ O V~ ~1 0
~: h ~:: S C~ ~ h ~ S ~ S~ h 1~
El ~ S o ~ ~ El ~ S O ~) ~ E~ ~ I h
o ~ O ~ Ei o ~
O O O
.,1
4~ ~ S
~ J ~ O O ~ , g
O O ~ 4~ ~ rl S
~: S C~
I I x a~
C CrL ~ V~ ~ ~ O ~ U~ S
g
0~ ~ ~0 i~ 3 3 ~0
O g ~ ~ N ~ ~ S Ei
~d ~ g 4~ Og ~ g ~
a o ~ o ~H o ~ o ~ o ~ o ,~ o ~t
~ ~ ~ s ~ s
_I
U~ Z; O O O O O O O
- 32 -
C
,,. .1
~1~!6`~9
~: O V~ h V~ h
~ 0 3 ~S 3 ~ 30 ~ o 3> ~
O ~ --~ t4 ~ ba ~ ~0 ~ ~4 ~ ~1)
o o ~ ~ ~ ~
~ O O ~ O ~
~ ~ ~ ~ 'o o~ a~ o g ~ o ~,
o ~ ,~ ~ oo ~ o ~> ~ ." ~ o c) ~ oo
E; o o I ~ o 5 0 ~ o ~ O ~ E3 o ~ o ~
O O V~ O ~D td r~ O ~ c~ ~ O ~D ~ rl
0 ~ '~ h o; I ~ 4
O ~ O ~ ~ o o ~ ~ ~ o o ~ O o
h ~ ~ ~ U) S h ~ S C~ ,In O ~ ~ Q, vl O ~ .C C~ U
,~ ~ h ~ O ~ ~i ~ h ~ ~ ~ ~ h ~ --I ~ ~ h ~ --
~ ~ ~ ~ d g ~o ~ ~ ~ O ,~ ~ e ~ g ~
O ~rl O I O ~ ~rl O I _I tt) ~rl 1.) I ~--I ~-1 ~rl C~
~J ~ ~ ~ e ~ qO
v, .~1 o ~ o tn rl O ~ O ~ o ~ o ~ rl O ~ O
~ h ~ ~ ~ ,C h ~ h ,C t~ h~ ~ ~d ,5 ~
~ ~ e ~ ~ e ~ ~ e ~ ~
~ I I
~ O ~ O O ' o O
o 't ~ t ~ t ~ a~ q
O ~ ~ ' e ~ ~ R
O R R ~ R ~ ~ N ~ ~d R ~d R
R ~ g ~ 40 ~ ~0 ~ O ~ 0 4~ 0 4
o ~ o ~ o ~ o ~ o :~, o ~ o ~ o :~
~ ~ e ~ e ~ ~i ~ e ~ ~ ~ e ~
N a) N O N a) N ~ N C> N In N ID N
N ~ ~ U~
O O
~C O _I ~1 ~ ~ ~ ~ ~1
L~Z - 33 -
C
':
a~
~ l ~
~ ~ ~ ~>
rC O vl h
~ 3 ~ ~ a~
h O O ~ b~ tlO b~ bl) la~ 1~1)
O ~ ~ bO
o ~ ~ h h h h h h
O :~ ~ h O O O O O O
+, ~ .
O ~ ~ O ~ O 1
~o ~o ~ 1 4
6 ~ 6 ~ 1~ 0 6 ~ ~
~ ~ 1-1 6 ~ ~ t~5 ~ 6 4l ~ ~ 6 ~H
1~ ~1 -1 1 6 t.~ 6
O o ~ t~ ~/ O v, n~ o u~
~ i ~ O
O O
~S ~3 o o ~ ~ ~ O O ~ O O ~d ~
~1) O ~ ~: V~ O ~ O ~ ~ ~: O
h r~ h ~ rl ~ ~ rl ~ ~ h rl ~ ,1
r-l ~p~I p~ O~
O O .C ~ '~ O rC ~ ~ ~ O rC
t~ I O ~ I O ~:
h ~ h C ~ ~ O
c6d 6~ 6 ~ 6 ~ 1
I ~ U~
I a) I I ~n I I I
O ~ O O I O ~ ~D
I ~ rl rl
I ~ ~> I I ~ I ~ C~
~ I rC O I I ~ I . O ~?
O ~ C~ ~ ~ ~ ~ ~ ~ ~ ~ Q~
~ ~ ~ ~ 0~ ~ ~e ~ ~ O
O .~
~ ~ e ~
O
O ~ ~~ O ~ O ~H ~ ~ O ~ ~ ~ ~
0 4~ 0 ~0 4~ o 4~ o ~ O ~ O ~d O ~'
v~ ~ v~ ~ ~ ~ ~ ~ ~ rd ~ ~ V) ~ u~ O
6 ,~: e ~ 6 ~? e ~ e ~ ,e ~ e '' e 4~
`D ~ 00 ~) O ~I N
X o ~, ~ , 1 T-~ r~l -1 ~1 '
Ul Z;
- 34 -
f~
r
rd
r~ o
n ~ rD bD ~ ~ ~ rd
r~l O ~ ~ S O 0 50 0
r~ o ~ r r~
d I o r r
r--l r~ ~ o r--l O ~ r--l ~Q CH
r-l ~ R ~; rO r~ R R 1~ r~O
r r~ r~ IA r-l ~ n u~ r~
r~ ~ rd I rd ~rl rd ~0 ~ rd r rd
rd ~ o C~l cd ,I rd aJ ~I C~J d ~ o O
d Sl ~r-l ~ ~ O d : ~ s~ ~ r
r-l F~ h ,s~ O ~r r ~ ho ~ r~ rO
@1 O ~ ~ r~ ) O r~ cd r l ~r~ r;~
o ~ co ~ ~1 ~ +, co ~ t ~ r~ r~ I
u~ r1 O r--l I rd rn r~ O r-l ^ H rn ~ O
C~ $1 ~ 1~ C~ R h 5~ r-l O R ~ ~
I h ~ F~ ~ ~ r--l a) Cd
~ rd rd -r~ 0 ~3 c~ rd rd rl o r-l ~: r. c ~rl
o ~ I c, ,5~ 1 ~ I Cd ~ ~ ~ I r~d
s:~ ~ O r--l
O rl O ~ O ~
~ t rH ~ rH rtH
,~ ~ ~ r
r ~ ~ 1 ~ s 9 ii o
cd to tH ~ rO rO r~ rO ri~ ~O r~ o r~
rn a) ~ o rn O U~ u~ n n ,r
r-l tO r-l rrd r tO rl ~ r~ ~ r~ r1 rt ~
C~ rn C~ rn C\l rn C\J r~ 1) ~ rH
~ ~i ~ U~ ~ CO ~ O
-- 35 --
.
r~
c3 C~
C O
u~ ~ a) a) a
h O bD bD
O C) r, rl r~ r~
O C h a) h h a> tl) h C~
O O h O O h h O h
qO .c~ ~,,, c) ~, c
r-l Ir\ O ~ r~ I O r o r~
ul o O u~ O C~ O C)
rlrl ~ r~ ~rl ~ ~ ~ 'rd ~ ~ ,~ r d t~ ~ .c u~
o~ C~ O ~ R ~0
r ~ ~ r~ r ~ rJ C G~
c~ ~ rl +~ r i ~ ~rl ~ q~ ri
R a ~ ~ R O ~ ~ ~ o u I
O rl c) I r i t~ rl ~rl- ~ r~ ~ ~rl ~rl O r~ rl rl O r~ ~1
~d O I r~ r~ h Lr~ R ~,r r~ r~
~o R~ ,~ R R ~ ~r ~ c u~ ~ ~R O
O ~ O q~ r c~ ~ O q~ O ~ ~ ~ ~
~> o C~ > O O ~ R ~ o o c~ R
a~
I ,~ ~ r,~ 4~ ~ ~r
4-1 ~r~ 4~ 0 I r~ ~
R '~ , X R
oR ~ o I ~ rt
,cl ~ ~ r 0 a) O ~ O +~
O R J 4-1 ~rl R ~,rRI 4o~ C ~ ,rR~
O ,1 1 ~ ,1 ,i R ~ rr~
t~ Ct 0 N r l ~ C\l r~ ,J~ td 0 ~1 0
~r 4 R41 ~ 40t d 4~40 ,~? 40 ~j~ 41 qO rt
~ O ~ ~ 0 ~
~ rl 4 rl ~rl ~) r rl rl rl r rt
C\J ~ Q CU ~C\l qt C\l Ul C`J ~d C~ a
a)
rl rl C~J X ~ (~ 1 r rt
X O
-- 36 --
'
.
Example 139
297 parts by weight of 2-aminophenol-4-~-sulfatoethylsulfone are
suspencled in a mixture of 1,400 parts by volume of water and 600 parts by
weight of ice and the suspension is then neutralized with about 76 parts by
weight of anhydrous sodium carbonate. 205 parts by volume of aqueous 5N
sodium nitrite solution are then added and, after clarifying, the filtrate is
allowed to run dropwise onto a mixture of 250 parts by volume of 31% strength
hydrochloric acid and 1,500 parts by weight of ice. The resulting mixture is
then stirred for 1 hour at 0-5C, a little excess nitrous acid is destroyed
with a little amidosulfonic acid and tlle pH is then adjusted to 5.5 - 6.0 with
about 130 parts by weight of sodium bicarbonate. This solution is allowed
to run into a solution of the secondary condensation product of 1/2 mole of
cyanuric chloride with 1/2 mole of 1-amino-8-naphthol-3,6-disulfonic acid and
1/2 mole of 2-amino-8-naphthol-6-sulfonic acid, which is prepared as follows:
92.5 parts by weight of cyanuric chloride are dissolved in 300 parts by vol-
ume of acetone with warming and the solution is poured at 15-20C into 2,500
parts by volume of water. A solution of 159.5 parts by weight of 1-amino-8-
naphthol-3,6-disulfonic acid and 60.5 parts by weight of aqueous 33% strength
sodium hydroxide solution in 750 parts by volume of water is then added at
about 20C and the resulting mixture is stirred for 10 minutes, after which a
solution of 119.5 parts by weight of 2-amino-8-naphthol-6-sulfonic acid and
47.5 parts by volume of aqueous 33% strength sodium hydroxide solution in
1,000 parts by volume of water and then 150 parts by weight of crystalline
sodium acetate are added. The mixture is stirred for a further 90 minutes at
20-25C. After the diazonium salt solution has been added, the coupling re-
action is carried out for about 15 hours at 10-20C, the pH value being kept
at 5.5 - 6.0 by adding about 69 parts by weight of sodium bicarbonate in por-
tions. After the coupling reaction has ended, 300 parts by weight of sodium
- 37 -
r~
æ~
acetate (crystalllne) and 247 parts by weight of crystalline copper sulfate
are introduced, the pH is adjusted to 5.0 with a little 5N acetic acid and
the mixture is kept at 50-55C for 1 hour. The dyestuff is then precipitated
by adding 4,000 parts by weight of potassium chloride and is filtered off and
dri~ed in vacuo at 60C. This gives a dark powder with which violet dyeings
and prints can be produced on cotton fabric. The dyestuff has the following
constitution:
Cl
0 ~ -0 NH ~ ~ NH ~N==-N
Ho353 S03H ~
12 2 2 3
CH2 2 3
Example 140
243 parts by weight of 6-~-hydroxyethylsulfonylbenzoxazolone are
introduced at 80-100C into a mixture of 225 parts by weight of 100% strength
sulfuric acid and 255 parts by weight of 95.5% strength sulfuric acid and the
mixture is then stirred for 4 - 5 hours at 142 - 147C. After the mixture
has been cooled to about 80C, it is added to a mixture of 1,500 parts by
weight of ice and 500 parts by volume of water and the diazotization reaction
is then carried out at 0-5C by slowly adding 200 parts by volume of aqueous
5N sodium nitrite solution. The reaction mixture is stirred for l hour at
0-5C, a trace of excess n~trous acid is then destroyed with a little amido-
sulfonic acid and the pH value is then adjusted to 5.5 - 6.0 by adding about
445 parts by weight of calcium carbonate. The diazonium salt is coupled with
the coupling solution described in Example 139.
The reaction mixture is stirred at room temperature for 16 hours,
r~
.
the pH value being kept at 5.6 - 6.1 by adding about 108 parts by weight of
calcium carbonate in portions. The mixture is then warmed to 70 - 80C and the
gypsum is filtered off. The latter is washed with hot water, 300 parts by weight
of crystalline sodium acetate and 248 parts by weight of crystalline copper sul-
fate are then added to the filtrate and coppering is carried out at 40 - 45C
and a pH value of 5.0 - 5.5 for 2 hours. The dyestuff is precipitated by adding
potassium chloride and is filtered off and dried. A dark dyestuff powder is
obtained with which violet dyeings and prints with excellent fastness properties
are obtained on cotton materials. The dyestuff has the following constitution:
Cl
D ~ i1`o NH N NH / ~:,~ N-==N
~ N===N ~,~ ~
CH2-025~J HO3S SO3H S03H S02CH2CH20S03H
CIH2
OS03H
Example 141
251 parts by weight of 2-aminonaphthalene-8-~-hydroxyethylsulfone are
introduced into 660 parts by volume of 20% strength oleum in the course of 20
minutes and the mixture is then warmed at 65-70C for 4 hours. The reaction
mixture is then cooled to 25-30C and allowed to run into a mixture of 2,500
parts by weight of ice and 1,000 parts by volume oE water. The diazotization is
then carried out at 0-5C with 200 parts by volume of aqueous 5N sodium nitrite
solution, stirring the reaction mixture for 1 hour at 0-5C, and a little ex-
cess nitrous acid is then destroyed by means of amidosulfonic acid. The pH of
20 the diazonium salt solution is then adjusted to 5.0 - 5.5 by adding 1,200 parts
by weight of calcium carbonate and the solution is combined with the coupling
solution described in Example 139. The coupling
- 39 -
' C
reaction is carried out at room temperature for 20 hours, the pEI value being
kept at 5.5 - 6.0 by adding about 90 parts by weight of calcium carbonate in
portions. The mixture is then warmed to 70 - 80C and the gypsum is filtered
off and washed with hot water, and 300 parts by weight of crystalline sodium
acetate and 247 parts by weight of crystalline copper sulfate are then added
to the filtrate. A mixture of 228 parts by weight of aqueous 30% strength
hydrogen peroxide and 1,000 parts by volume of water is then added dropwise
at 35-41C in the course of 40 minutes and the resulting mixture is stirred
for 4 hours at 35-41C. The dyestuff is then precipitated by adding potas-
sium chloride-and is filtered off and dried. This gives a dàrk powder with
which reddish-tinged blue dyeings and prints are obtained on cotton mate-
rials. The dyestuff has the following constitution:
OSO3H
CH2OSO3H Cl Cu IH2
02S O ~ ~ O NH ~ N ~ H ~ ~
E103 ~O~S SO3H SO3H ~ SO3H
Example 142
325 parts by weight of 2-methoxy-5-methyl-aniline-4-J~-sulfatoethyl-
sulfone are suspended in 1,500 parts by volume of water and 500 parts by
weight of ice and dissolved by adding about 64 parts by weight of calcined
sodium carbonate, the resulting pH value being between 6.0 and 6.5. 203 parts
by volume of aqueous SN sodium nitrite solution and 15 parts by weight of
kieselguhr are added and the solution is clarified. The filtrate ia allowed
to run at 0-5C into a mixture of 1,500 parts by weight of ice and 282 parts
by weight of aqueous 31% strength hydrochloric acid. After the mixture has
- 40 -
been stirred for 1 hour at 0-5C, excess nitrous acid is destroyed with
amidosulfonic acid and the pll of the resulting diazonium salt solution is
then adjusted to 6 by introducing about 40 parts by weight of sodium bicar-
bonate. Tllis solution is coupled with the coupling solution described in
Example 139 and the reaction mixture is stirred at 18-22C for several hours,
the pH value being kept at 5.3 - 6.2 by adding sodium bicarbonate in portions.
After the coupling reaction has ended~ a solution of 346 parts by weight of
crystalline copper sulfate, 483 parts by weight of crystalline sodium acetate
and 318 parts by weight of glacial acetic acid in 1,475 parts by volume of
water is added and the resulting mixture is then boiled under reflux for 20
hours. After cooling, the dyestuff solution is clarified and the dyestuff
is then precipitated by adding potassium chloride and is filtered off and
dried. This gives a blue-black powder with which cotton materials can be
dyed in violet color shades. The dyestuff has the following constitution:
C1
O ~ ~ H~IH~===N~S02CH2CH20S02H
CH2-CH2-2-5 ~ ;N ~ S03H S03H CH3
Example 143
If, in Example 139, the solution of the coupling component is re-
placed by the solution described in Example 2 and in other respects the same
procedure is followed, a dark brown dyestuff powder is obtained with which
ruby-red dyeings and prints can be produced on cotton materials. The dye-
stuff has the following constitution:
- 41 -
~.~
t~`3~
SO3H
Cu Nll / Cu
llO NH N HN S03H ~
S~)2 3 ISO2
Cl~2 CIH2
GH2-OS03H CH2-OS03H
Example 144
The non-metallized dyestuff is prepared as described in Example
139. After the coupling reaction has ended,the coupling solution is warmed
to 55-60C and, at this temperature, 320 parts by weight of crystalline sod-
ium acetate and 250 parts by weight of chromiuTn potassium sulfate are added.
The temperature is then raised to the boiling point and the mixture is boiled
under reflux for 6 hours. The dyestuff solution is clarified and spray-dried.
This gives a dark grey dyestuff powder with which grey-violet prints can be
produced on cotton fabric. The dyestuff has the following constitution:
C ' ~¢~5 ~i
C1112 CH2-OS03H
C~l2-OS03~l
Example 145
The non-metallized dyestuff is prepared as described in Example 140.
After separating off the gypsum, 300 parts by weight of crystalline sodium
- 42 -
r~
~,. ~
acetate and 295 parts by weight of crystalline cobalt sulfate are added to
the dyestuff solution and the mixture is then warmed at 60 - 65C for 2
hours. The dyestuff solution is clarified and then evaporated to dryness in
vacuo. This gives a dark dyestuff powder with which opaque violet prints
with excellent fastness properties can be obtained on cotton materials. The
dyestuff has the following constitution:
Cl
/ C/2 ~ ~ N ",Co/2 0
O NH N 1 Nll ~ N===N ~
CH2 C 2 2 3 S03H 3 S02CCH2
OS03H I 2
OS03H
The heavy metal complex dyestuffs listed in the table which follows
can be obtained in a manner similar to that described in Examples 139 - 145.
In the "diazo component" column, the said components are described in the
form in which they are present after metallization, that is to say in some
cases with a hydroxy group formed from a methoxy group by demethylating metal-
lization or with a hydroxyl group introduced by oxidative coppering.
- 43 -
. .~
h ~ O E ~3
O ~ ~ 3 ~ ~ ~ .,1 ~ ~ ~ ,
r~ ~ ~) O O O O h O O O O
O ~ O h F;l D ' ' ' ~~
~ ~ E~
E ~: D .~ . E
a) ~ o
~ O; ~
~,5
O ~ ~4~ 0
~ ~ 3 ~ O ~1 40
t~O ~ ~ ~
~ h,~ I ~ h S
C~ h ~ O h
O ~ 1~ ~ O t~
E E ~ o
~0 ~1 41 ~0 E3 0 4
O 0 4~ O O
~L I I I
d- U) S ~ S S
1:: ~ O S o ~ ~ S ~1
~ o ~ 0 4~ ~; ~
O rl ~ O ~ ~ O r~ ~
N ~ h 4~ ~ I C ~ ~ ~?
td ~ ~ cd .-1 D ~ e
S ~ S ~ V)
4~ ~ ~40 ,s, o U~ ,-~
td ~ O
. ~ ~ ~ ~ ~ o~ ~ ~ O ~ O ~ ~ U~
o ~ ~ ~ 2 ~H e ~ ~
a~
D ~ ~ ~D I~oo a~ O ~ ~1
~d X O
E~ ~ Z
- 44 -
.
`
.
f~
h C> o ~ 3 r-l 3 r~
r1 C~ ~ O O O O O O O O O O O O
O ~ O ~h ,D r ~ , r . r r ~ ~ . r r
X ~ ~) rl ~ h h
r-l . r~ r-l ~3 r1 C) a> Ei r~
h ~P~ ~ h ~ ~
O O O ~ O O O ~: O ~ O
~ t~ I o
r1 ~ g r1 0 Vl
6 N r r~ I; ~ I
g ~o '3 1` ~0 ~ t"
r~ 1) 0
~ ~1 C~ O r-l rl
t~ ~ h ~ - h ~
~: h r~ ~P h r~
r 1 1~
O t_~ I O ~
O .rl rl O .rl .r~ O r~
n~ ~ ~ hr O
O ~ 0 4~ 4~ 0
O O ~d ~ O o 4~ u~
a
L In
r-l r~ r1 r-l r I
F F F F F F
~ r Ei r _ ~ r ~ r _ _ E~ r _
a ~o o ~ ~0 ~ 40 s 40 ~
o ~ o tn o o o
0 4~ ~0 ~ 0 4~
~ V
r-1 ~ t~
U~ U') U~ ~ U'~ U~ U~
_l ~ ~ ~ ~ ~ ~ ~1
Z
- 45 -
3 5 ~
h ~ O , ,~
1:: ~ O O ~ ,D h o ~ O h h
O .C O . ~ . . ~ ~ ~ O h O O
t~l
X ~ h ~ h ~ h r~ ~ h rl
~ o ~ ~ ~ ~ O ~ O
I O
0 ~ O ~
~`D ~ ~ ~ ~ ~ ~0
O ~O ~d o 3
~P ~- o o ~ a> o (~
O ~ ~ _ _ ~ h ,S O ~
bl) O O P~ ~1 ~ O O P~ O
h ~ t
~1 ~,5~ U) ~.C
O rl ~ O ~ ~1 ~0 ~ I
h ~
~ 0
~ I ~ N ~
~ O 0 4~ O O ~
~ I ~
O I I I I I
O
~ O t~ N .~I .Ç I ,~ ~ ~>
S: ~ .C I ~ N ~ N ~ ~ ~
O ~ ~ ~ S ~ h ~ ~ O R
O ~ 6 ~ ~ ~ 5 4
~ _l U~ ~ ~ C~ O
V~ -~ n U) IUl I U~ I 11) 0 U~ O
o ~ o ~ ~ ~o ~ a~ ~o ~ c) ~o 41 ~
F~ S ~ e ~
~ S ~~ 4~
~ ~ ~ ~ ~ ~ ~ ~ ~`
O
Z;
- 46 -
. .
~6~g
g
O ~ ~> O O ~ OO o O ~ O ~d O O
O ~ O h ~ ~1 h ~1h rl ,1 h rl ~.,~
ul ~ ~ 0 ~ O :~ ~ h '
_I ~ h ~ ~ ~ h ~ ~ h h
p., ~ O cd ~ O ~d
O ~ ~ ~ .C '9P' ~ ~ ~4
a> ~
~ E~ O I ~ E3 ~ ~
O ~ ~ O rl
'I ~ O
O 3, ~ t~ 0 3 1
,C ~ _ _ _ _ _
h rC O ~ ~ h ~ ~ 4
~:: ~ R 4
O t~ g ~
O rl r~ O ~ I~ r~ rl O ~ ~
rl ~ E3
g 4~ ~ t.~ ~ 0 41 ~H ~0 ~
O O ~ O 0 4~ 00 ~1
~, ~L ~ I ~_1
,J ,5 ~ O,
O~ ~ O ~
~ Cll R ~ 2 ~ ~ o
~o ~ ~ ~o ~ ~o ~ ~o ' ~o ~ ~
~ ~ ~R ~ o ~ ~ R
n ~ I~ oo a~ o
~X o ~ ~ ~ I~ ~ ~ ~ ~ _I
~Ll Z
- 47 -
r~
. ~
O ~ ~ ~ ~ ~
o ~ o o o o o
o ~ o
h h h h h
h O O
O ~ V
a~
~ _~ ~1 ~1 ~
G~ O ~ > O ~ I ~ rl
o ~ o
~ 3
g ~ ~ ~ ~ N ~ 0 3 ~ ~ t~ a
O ~ ~ ~ ~ O
d h ~ ~1 ~
C: p,"~ h .C ~ ~ 5 'E;
O ~ O ~ rl O ~ ~
C~ ~ h ~ 0 4-1
e
o 0 4~ O 0 4
C~ ~ ~ O
'
N ~
~ ~O ~ ~ O
Ei ~ 6
1~1 ~ ~1 ~ ~1 ~ ~ N ~1 ~ u
~1 O ~ O ~O ~ O ~ O I
U~ O U~ o U7 o tl~ o U~,
a) ~ 1 0
0 4~ 0 ~H 0 4~ 0 4~ 0 S::
N U~ ~ Vl ~ v~ ~ Ul ~1 p~
~ ~
X
L4 Z
- 48 -
:
.
.
3~
Example 186
531 parts by weight of the dyestuff of the formula
OH
HO3SO CH2CH2 2 ~ N===N ~ ~ ~
H03S NH2
are dissolved in 3,700 parts by volume of water, the pH value of the solution
being adjusted to 6.4 - 6.7. A solution of 92.3 parts by weight of cyanuric
chloride in 300 parts by volume of acetone is then allowed to run dropwise ::
into this dyestuff solution, the temperature being 20-22C. The reaction mix-
ture is stirred for 15 minutes, the pH value is then adjusted to 6.4 - 6.8
with sodium bicarbonate, 150 parts by weight of sodium acetate are added and
the resulting mi.xture is then stirred for 1 hour at 55C. The dyestuff is
precipitated using potassium chloride and is filtered off and dried in vacuo
at 60C. It corresponds to the dyestuff listed under Example 72 in Table 1.
Example 187
306 parts by weight of the dyestuff of the formula
HO NH2
H35-CHzCHz~25 ~rN=- N ~`503H
are dissolved in 1,800 parts by volume of water and the pH value of the solu-
tion is then adjusted to 6.5 - 6.7. A solution of 92.25 parts by weight of
cyanuric chloride in 300 parts by volume of acetone is then added dropwise to
this solution and the resulting mixture is stirred for 15 to 20 minutes at
18-21C. The pH value is now adjusted to 6.4 - 6.8 by adding sodium bicar-
bonate and the mixture is again stirred for 15 minutes, a solution of 266
parts by weight of the dyestuff of the formula
- 49 -
,C
OH
~io3so-cH2cH2-o2s ~ ,~
HO3S
in 2,000 parts by volume of water and 150 parts by weight of crystalline
sodium acetate are then added and the resulting mixture is stirred for 1 hour
at 55-60C. The dyestuff is precipitated by adding potassium chloride and is
filtered off and dried in vacuo at 60C. It corresponds to the dyestuff
listed under Example 3 in Table 1.
Exampl.e 188
If the solutions of the two aminomonoazo dyestuffs of Example 187
are reacted with an aqueous solution of the primary condensation product of
1/2 mole of cyanuric chloride with 1/2 mole of ~-sulfatoethylamine instead of
with cyanuric chloride and the first reaction is carried out at 40-45C and
the second reaction is carried out at the boil, the pH being 5.8 - 6.5 for
both reactions, a dyestuff is obtained which corresponds to that listed in
Example 56 of Table 1.
The dyestuffs listed in Examples 1 and 2, 4 to 55, 57 to 71 and 73
to 138 can also be prepared in a manner similar to that described in Examples
186 to 188.
Example 189
345 parts by weight of the dyestuff of the formula
''~' ~ O H
B0 HO SO-CH CH -U2S ~ N===N ~
~ HO3S S03H
are dissolved in 3,000 parts by volume of water, the pH value being adjusted
to 6.4 - 6.8 with a little sodium bicarbonate.` A solution of 92.5 parts by
- 50 -
l~
weight of cyanuric chloride in 300 parts by volume of acetone is allowed to
run dropwise at 15-25C into this dyestuff solution and the mixture is then
stirred for 30 minutes at the indicated temperature. The p}l value of the re-
action mixture is then again adjusted to pl-l 6.4 ^ 6.8 with a little sodium
bicarbonate and the ~ixture is stirred for a furtherl5 minutes. A solution
of 305 parts by weight of the dyestuff of the formula
O ~Cu
Ho3so-cH2cH2 2 ~ N-==N ~ ~ 2
H03S
in 3,000 parts by volume of water and also 150 parts by weight of crystalline
sodium acetate are now added and the mixture is then stirred for 2 hours at
50 - 55C. After cooling to 18 - 20 C, the dyestuff is precipitated with
potassium chloride and is filtered off and dried in vacuo at 60C. It cor-
responds to the dyestuff indicated under Example 140.
Example 190
If the solutions of the two aminomonoazo dyestuffs of Example 189
are reacted not with cyanuric chloride but with an aqueous solution of the
primary condensation product of 1/2 mole of cyanuric chloride and 1/2 mole
of taurine and the first reaction is carried out at 40 - 45C and the second
reaction is carried out at the boil, the pH being 5.8 - 6.5 in both reactions,
a dyestuff is obtained which corresponds to that listed lmder Example 176
in Table 2.
The copper complex dyestuffs further listed in Examples 140, 141 to
143 and in Table 2 can also be prepared in a manner similar to that in Ex-
ample 189 and 190.
Example 191
306 parts by weight of the dyestuff of the formula
I r~
110 NH2
1-103SO-cl12cH2-o2s~ ~
ilo3s SO3H
are dissolved in 2,000 parts by volume of water, the pH value of the solu-
tion :is then adjusted to 6.4 - 6.8 with a little sodium bicarbonate and a
solution of 92.5 parts by weight of cyanuric chloride in 300 parts by volume
of acetone is then added dropwise to the dyestuff solution. The reaction
mixture is warmed to 35-40C and kept at a pH of 6.3 - 6.7 for 45 minutes by
adding sodium bicarbonate in portions. A solution of 266 parts by weight of
the dyestuff of the formula
~ N===N ~ ~ NH2
HO3SO CH2 2 2 HO3S
in 2,000 parts by volume of water, the pH of which has previously been ad-
justed to 6.4 - 6.8, is then added and the reaction mixture is warmed to
60-65C, thepH value being kept at pH 6.3 - 6.7 by adding sodium bicarbonate
in portions. When no further starting dyestuff can be detected in a paper
chromatogram, thedyestuff solution is clarified and the dyestuff is isolated
by spray-drying. This gives a red powder with which red dyeings and prints
can be produced on cotton in the presence of acid-binding agents. In the
form of the free acid, the dyestuff has the following constitution:
N ~ N
HO NH ~ N ~ NH
~ I ~Y~' ~ ~N===N ~
H03SO 2 2 2 ~ ===N ~ I ~ ~ SO3H SO2CH2CH2
HO3S SO3H OSO3H
- 52 _
; ~
3~
Example 192
If a solution of 344 parts by weight of the dyestuff of the formula
O ~ ~ o NH
H03SO-CH2CH2 2 ~ N===N
HO S
3 S03H
in 2,000 parts by volume of water is used in place of the first dyestuff so-
lution in Example 191 and in other respects the same procedure is followed,
this gives a dark dyestuff powder with which cotton materials can be dyed and
printed in brown-violet shades. In the form of the free acid, the dyestuff
has the following constitution:
OH2CH2-025 ~ N==-N ~ ~ N~ N-==N ~
OS03H H 3 S02CH2CH2
S03H OS03H
Dyestuffs which contain two different diazo components, for ex-
ample those indicated in the table which follows, can be prepared in a con-
trolled manner by a method similar to that indicated in F.xamples l91 and 192.
- 53 -
C
68~
a~
O h
C ~ ~ h
:C N o cN
~N O ~ ~ V~
~_ Z o~ O
0~
~ $ z~
. ~ Z~
o~ o~
Z o~ Z~ o~
O ~ O ~" O :C
~ o ~ ~ O
~ ~
~ ~ z
- 54 -
~; ~
a~
~ o
v~ ~
~ ~ r, ,, o
o~
:~
~ ~ o ~
x x u) ~)
~-- ~--0 N
O
U~
11 X Z;
11 ~ 11 X
Z 0 11 0
,C:
~ ZX ZX;
7=( x , 7~=~
X_4~ Z
''\r\~Z, x / ~
0~ \r\ '' x
~ O ~0~
N N O
U--~--O
æ ~ c~
- 55 -
a~
rc o
h O 3
O O h
3~
O O
T'~
Z o~ ~Z
Z
/~ ~
\ \ Z Z
~ , ~
0~ :C O ~::
I ~ I
' X~ ~ U
O ~ O
~ o~
Z O~
- 56 -
