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Патент USA US3060191

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‘atent
EQQ
3,060,18
Patented Oct. 23, 1962
1
2
3,060,180
As aryl-carboxylic acids there are advantageously used
those of the formula
ANTI-IRAQUINONE VAT DYESTUFFS CONTAIN
ING CHLORO-TRIAZENYL GROUPS
Max Staeuble, Base], and Kurt Weber, Bottmingen, Switz
erland, assignors to Ciba Limited, Basel, Switzerland
N0 Drawing. Filed May 26, 1959, Ser. No. 815,785
Claims priority, application Switzerland May 30, 1958
6 Claims. ((31. 260-249)
This invention provides valuable new anthraquinone
(3)
N
A
lltt
h
vat dyestuffs which contain at least one aroylamino group 10
and at least one group of the formula
in which aryl advantageously represents a benzene radi
1)
cal, n and p each represent the whole number 1 or 2, and
X represents a hydrogen atom or a substituent. As suit
O-X
15 able substituents there may be mentioned chlorine atoms, '
alkyl, phenyl, hydroxyl, alkoxy, hydroxyalkoxy, aryloxy,
especially phenoxy, primary and secondary amino groups,
for example, an —NH2 group, a mono or di-alkylamino
which is bound directly or through a bridge member to
group, for example, mono- or di-methylamino group,
an aroyl residue, and in which X represents a hydrogen 20 mono-or di-ethylamino group, a monobutyrylamino
atom or a substituent. Advantageously, the new com
group, ethylene-imino group, mono- or di-B-hydroxyethyl
pounds correspond to the formula
amino group, monochloroethylamino or monocyanethyl
(2) i
amino group, mono- or di-carboxymethylamino group,
N
or arylamino group, for example, an anthraquinonylamino
25 group, and especially a phenylamino group, which may
be substituted in the phenyl radical, advantageously by a
hydrophilic group, for example, a carboxylic acid, sulfonic
acid, sulfonamido, alkyl-sulfone or alkoxy group, and
El
also groups capable of being converted into hydrophilic
in which A represents an anthraquinone radical, m and n 30 groups, for example, sulfo?uoride, sulfochloride, car
each represent the whole number 1 or 2, and X has the
boxylic acid chloride, sulfonic acid ester or carboxylic
meaning given above.
acid ester groups. The symbol X may be an alkylmer~
\O/
(51
The invention also provides a process for the manu
capto or arylmercapto group, for example, a methylmer
facture of the above new dyestu?s, wherein an amino
capto, carboxymethylmercapto, ethylmercapto or phenyl
anthraquinone is reacted with a reactive derivative, more 35 mercapto group.
especially a chloride, of an aryl carboxylic acid which
As examples of suitable aryl carboxylic acids of the
Formula 3 there may be mentioned: 2-carboxyphenyl
contains at least one group of the Formula 1 bound
directly or through a bridge member to an aroyl radical,
and, when the resulting reaction product contains a di
amino-4:6 - dichlorotriazines,
chlorotriazine radical, if desired, exchanging one chlorine 40
atom for a substituent containing at least two atoms.
ylarnino-6~chlorotriazines, 2-carboxyphenylamino-4-ethyl
ene-imino - 6 - chlorotriazines,
As aminoanthraquinones suitable for the process of
this invention there may be mentioned monoamino- and
2 - carboxypheny1amino-4
amino-6-chlorotriazines, 2-carboxyphenylamino-4-dimeth
2:4 - di - (carboxyphenyl -
amino) -6-chlorotriazines, 2 - carboxyphenyl-4:6-dichloro
triazines, 2:4-di-(carboxyphenyl)-6-chlorotriazines and
also diaminoanthraquinones, for example, l-aminoanthra
2 - (3':5' ~ dicarboxyphenylamino)~4-a1nino-6-chlorotri
quinone and simple substitution products thereof, such, 45 azine.
for example, as 1-amino-4-methoxy-anthraquinone, 1
The reaction of the aminoanthraquinones with the re;
amino-4- or -5- or -8-acylamino- and especially -benzoy1
active derivatives, especially chlorides, of arylcarboxylic
4 amino-anthraquinones. The latter may be substituted in
acids is advantageously carried out in an inert organic
‘the benzoyl radical, for example, by a halogen atom,
methoxy, alkyl, tri?uoromethyl, sulfonamido or alkyl 50 solvent, for example, nitrobenzene, chlorobenzene or
sulfone group. There may also be mentioned 1:5- and
ortho-dichlorobenzene, at a raised temperature. Aryl
1 : S-diaminoanthraquinone and l :5-diamino-4 : 8-dioxy
monocarboxylic acids of the Formula 3 are advanta~
anthraquinone. There may also be mentioned those
geously reacted in the molecular ratio 1:1 with the mono
aminoanthraquinones which contain a further fused-on
aminoanthraquinones or in the molecular ratio 2:1 with
carbocyclic or heterocyclic ring, for example, 4-amino 55 the diaminoanthraquinones. Aryldicarboxylic acids of
anthraquinone-2: 1- (N) -acridone, 5 -amino-1 :9-isothiazo
leanthrone, 4- or S-aminoanthrapyrimidine, mono-amino
the Formula 3 are advantageously reacted with mono
or diamino-acedianthrones, 4- or 5-amino-1:1'-dianthri
When there are used as starting materials those aryl
carboxylic acids of the Formula 3, in which X represents
aminoantharquinones in the ratio 1:2.
mide-carbazole, 4:4'- or 5:5'-diaInino-l:1’-dianthrimide
carbazole, 4- or S-amino-S’-benzoylamino-dianthrimide 60
carbazole or 4-amino-4'-benzoylamino-dianthrimide-car
bazone, 4-amino-anthrapyridones, amino-dibenzanthrone,
amino - isodibenzanthrone,
aminodibenzpyrenequinone,
aminoanthrathrone, aminobenzanthrone, amino?avan
throne, and also the compound of the formula
(I)
NH“
0
some“
I!
a chlorine atom, that is to say compounds which contain
a dichlorotriazine radical, a chlorine atom in the arylide
so obtained may be exchanged for a substituent contain
ing at least two atoms, for example, a hydroxyl, alkoxy,
65 hydroxyalkoxy or aryloxy group or one of the primary
or secondary amino groups or mercapto groups men
tioned above.
The invention also includes a modi?cation of the proc~
ess described above, wherein an anthraquinone of the
70 formula
8,060,180
'
4,.
3
Example 1
is condensed with a compound of the formula
3.9 parts of the triazine derivative of the formula
(5)
N
Cl—-(|J//N\ \?—x
/N
5
\‘f
l
01
in which X has the meaning given above, and, when the
reaction product so obtained contains two chlorine atoms
in the triazine radical, one chlorine atom is exchanged
for a substituent containing at least two atoms. Thus,
or
10 are suspended in 100 parts of dry nitrobenzene and con
verted into the corresponding dicarboxylic acid chloride
with 4 parts of thionyl chloride by being stirred at 100
to 105° C. The excess thionyl chloride is removed from
the clear solution in vacuo, and 6.9 parts of l-amino-S
for example, one molecular proportion of the compound‘ 15 benzoylamino-anthraquinone are then added. The term
of the Formula 4 may be reacted with one molecular
perature is raised to 160 to 170° C. and the whole is
proportion of cyanuric chloride, and the resulting dichlo
rotriazine reacted, if desired, with a primary or secondary
amine, or two molecular proportions of a compound of
stirred on for 3 hours at the same temperature.
After
cooling, the orange-colored suspension of the new dye
stu? of the formula
C
a
A iIH-oC-O
the Formula 4 may be reacted with one molecular pro
portion of cyanuric chloride.
The dyestu? so obtained may be isolated from the me
dium in which they are produced and, notwithstanding
the presence of an exchangeable halogen atom, they can
be converted into useful dry dyestu? preparations; The
dyestuff is advantageously isolated by ?ltration. The
?ltered dyestulf may be dried, if desired, after the addi
tion of a neutral or weakly alkaline extender. Advanta
geously the drying is carried out at not too high a tem
perature, if desired, under reduced pressure.
The new dyestulfs are suitable for dyeing a very wide
variety of materials, and especially for dyeing or printing
is ?ltered off, washed with nitrobenzene and then with
alcohol and ‘dried in vacuo at 60 to 70° C.
A dyestu?f powder is thus obtained which is yellowish
35 brown when dry; it dyes cotton and regenerated cellulose
by the dyeing method described in Example 19 orange
yellow tints of very good fastness properties. The dye
stuif is so securely ?xed on the fiber that the strength
of the dyeing is not substantially impaired even by a
treatment with a hot organic solvent, such as dimethyl
formamide or pyridine.
The
2:4 - di - (carboxyphenylamino) - 6-chlorotriazine
used as acylating component in this example can be pre
pared, for example, by condensing equimolecular propor
textile materials of natural or regenerated cellulose by 45 tions of the sodium salt of 4-aminobenzoic acid and cy
the usual vat dyeing or printing methods.
anuric chloride in the molecular ratio of 2:1 in an aque
As the reactivity of the halogen atom in the triazine
ous medium at a temperature ranging from 0 to 40° C.,
ring varies somewhat from compound to compound it
by continuing the condensation at a slowly rising temper
is of advantage to adapt the method of dyeing, that is
ature until aminobenzoic acid can no longer be detected.
to say especially the concentration of the alkali or reduc 50 To isolate the dicarboxylic acid derivative it is advan
ing agent, and the duration and temperature of the dyeing
tageous to adjust the pH value of the aqueous suspension
or steaming operation, to suit the dyestutf used. The
with dilute hydrochloric acid to 2, ?ltering off the pre- _
most favourable conditions can easily be determined by
preliminary tests.
cipitate thus ‘formed, washing it with water until free
In contradistinction to the conventional vat dyestu?’s, 55 from acid and drying it in vacuo at 70° C.
the dyestuffs of this invention are substantially irremov
Example 2
able from the ?ber with hot dimethyl formamide so that
it is probable that they are chemically bound on the ?ber.
15.4 parts of 2:4-bis-(4'-carboxyphenylamino)-6-chlo
Dyeings produced with the dyestu?s of this invention
ro-1:3:5-triazine are heated in 300 parts of nitrobenzene
are fast to dry cleaning and migration. The dyed fabrics
can therefore be coated with synthetic resins, for example, 60 with 24 parts of thionyl chloride and 3 parts of dimethyl
.formamide with stirring for 1 hour at 120° C. The excess
polyvinyl chloride, without the dyestutf migrating into the
thionyl chloride is distilled off in vacuo, at 100° C. 20
arti?cial resin. This is especially important in the manu~
parts of l-aminoanthraquinone are added, and the mix
facture of arti?cial leather.
ture is heated for 3 hours at 120° C. The dyestutf of
The following examples illustrate the invention, the
parts and percentages being by weight.
65 the formula
N
/
N
N
61
3,060,180
5
6
is isolated in the usual manner; it dyes cotton and regen-
I
Example 4
erated cellulose by the method described in Example 20
,
yellow tints having good fastness- properties_
.
_
_
_
3.9 parts of the triazine derivatlve of the formula
The corresponding dyestutl from l-amino-4-benzoyl
aminoanthraquinone ‘gives red dyeings of similar, good '5
properties.
HOOC_®
I When in the above example the l-aminoanthraquinone
is replaced by an equimolecular amount of 1-amino-6:7dichloroanthraquinone, an orange-yellow dyestu? of very
good fastness properties is obtained.
N
1lIH_O/
\C_NH_QOOOH
II
|
N\ /N
10
0
Example 3
371
3.9 parts of the triazine derivative of the formula
HOOC
N
/ \
NH-fJ
000E
are suspended in 100 parts of trichlorobenzene and con
verted into the corresponding dicarboxylic acid chloride,
15 by being stirred at 100 to 105° C. with 4 parts of thionyl
(|3—NH
chloride. 6.9 parts of 1-amino-S-benzoylamino-anthra
N
\C%
6
1
quinone and 0.1 part of dimethyl formamide are added,
the temperature is raised to 160—170° C. and the whole
is stirred on at this temperature for 3 hours.
20 After cooling, the dyestu? of the formula
H
\O%
Goo-11111 0
(‘J1
0 NH--O o-O
are suspended in 70 parts of dry nitrobenzene and con-is ?ltered off, washed with trichlorobenzene and then with
verted into the corresponding dicarboxylic acid chloride
alcohol, and dried in vacuo at 70—80° C.
by being stirred at 110° C. with 4 partsof thionyl chloThe dyestutf dyes cotton and regenerated cellulose by
ride. The excess thionyl chloride is removed from the 40 the method described in Example 19 yellow tints having
solution in vacuo, and 6.9 parts of l-amino-S-benzoylvery good fastness properties.
aminoanthraquinone are then added. The temperature
The acylating component used in this example can be
is raised to 160° C., 0.1 part of pyridine is added, and
made, for example, in the following manner:
the mixture is stirred on for 1 hour at 160° C. After
Equirnolecular amounts of the sodium salt of 3-arnin0
cooling, the new dyestutl of the formula
45 benzoic acid and cyanuric chloride are condensed in the
? NH-OOQ N C>O°~NH ?
\
I1IH—-(“3/N\ /N\o-rlrn
I
<:>-oo—Nn b
O/
61
II
o rim-00G
is ?ltered off, washed with nitrobenzene and then with
molecular ratio of 1:1 in an aqueous medium at 0-5° C.
alcohol and dried in vacuo at 80° C.
60 On completion of the monocondensation, 1 molecular
Cotton and regenerated cellulose are dyed by the
proportion of 4-aminobenzoic acid is added in the form
method described in Example 19 yellow tints having very
of a neutral aqueous solution of the sodium salt and con
good fastness properties.
densation is performed at a temperature rising to 40° C.
The acylating component used in this example can be
until aminobenzoic acid can no longer be detected. To
prepared, for example, by condensing equimolecular 65 isolate the asymmetrical dicarboxylic acid derivative the
amounts of the sodium salt of 3~aminobenzoic acid and
reaction mixture is acidi?ed, and the product is ?ltered
cyanuric chloride in the molecular ratio of 2:1 in an aqueous medium at a temperature ranging from 0 to 45° C.,
o?, washed with water and dried in vacuo at 70° C.
Example’ 5
by continuing the condensation at a slowly rising tempera-
-
.
ture until aminobenzoic acid can no longer be detected. 70
3.4 parts of 2-(4'-carboxyphenylamino)-4-amino-6
To isolate the dicarboxylic acid derivative the pH value
chloro-1z3z5-triazine are suspended in 50 parts of dry
of the solution is advantageously adjusted to 2 with dilute
nitrobenzene and 1.0 part of dirnethyl formamide, and
hydrochloric acid, and the precipitate formed is ?ltered
3.0 parts of thionyl chloride are stirred
The mixture
off, washed until free from acid and dried in vacuo at 60
is heated at 90-100° C. until a clear solution of the acid
to 70° C.
75 chloride is obtained.
3.4. parts of l-amino-S-benzoyl
3,060,180
8
amino-anthraquinone are then added.
The temperature
'
is raised to 125 to 130° C., and the whole is stirred for a
further'6 hours at this temperature, cooled to room tem
I
11
111
perature and the dyestutt of the formula
0
N
o
5
NH-O O-ONH-O/ \C—Cl
NH,
H
1 """ "
C1
°’§§§§;,_
1'l\ g.
(I3/
NH:
'
1 ‘
0
l
C>~o
o-NH o
'
H '
0
2 ______ __
p
H
7
yellow.
(I;
/ \
is ?ltered o?f, washed with methanol, and dried at 70° C.
1E1
III
The dyestu? produces on cotton and regenerated cellu- 15
lose by the method described in Example 21 very fast
orange-yellow prints.
The
2-(4'-carboxyphenylamino)-4 - amino - 6 - chloro
lz3z5-triazine used in this example can be prepared by
condensation in an aqueous medium of a ?ne suspension 20
of 2-amino-4z6-dichloro-l z3z5-triazine and the sodium
IT
II
Hm
O
.
3 ------ --
yellow
salt of 4-aminobenzoic acid in the molecular ratio of 1:1
([1)
NH‘O C®—NH”
at 30—40° C., or by ?rst condensing cyanuric chloride
and the sodium salt of 4-aminobenzoic acid in an aqueous 25
medium at 0-4° C. to form 2-(4'-carboxyphenylamino)
4:6-dich1oro-l : 3:5-triazine and reacting a further chlorine
atom at 30-40° C. with a slight excess of ammonia.
g
Equally good results are obtained by using as the acylat
ing component 2-(4’-carboxylpheny1amino)~4-dimethyl- 3o ‘1------ -arnino-6-chloro-1z3z5-triazine of the formula
N
?
I‘IIH?
0
/ \
“it
\
HOOO@—~NH—(§/ \(!:—o1
N
\ //
N
Ted
‘iONm
N—N
35
ii
‘i
‘
_
N(CH3)”_
Example 6
$3.25- (t4- - Farbogytgheélylamlmo)A'dlethylammoé'chlom‘ '
' ' ' nazme o
6
0mm a
. p
40 chloro-1:3:5-triazine are converted into the correspond
/N\
HOOC—<:>~NH—-G
IL];
3.2 parts of 2-(4'-carboxyphenylamino)-4-amino-6
ing carboxylic acid chloride in 100 parts of nitrobenzene
C—Cl
11;
with 2.5 parts of thionyl chloride at 95—100° C. The
solution is treated with 0.2 part of pyridine and then with
\ //
1.4 parts of l:5-diarnino-4:S-dihydroxyanthraquinone,
('3
45 and the temperature is maintained at 120—125‘’ C. for
N03213:):
2 hours with stirring. The mixture is then heated for 1
These acylating components can be prepared in a manner
hour at 150~l55° C., cooled to room temperature, and
similar to that described in this example for the prepara- _
the dyestu? of the formula
tion of .2-(4'-carboxyphenylamino)-4-amino-6 - chloro-
is ?ltered o? and dried.
1:3:5-triazine, by condensing the sodium salt of 4-amino- 65 a The; dy?stu? dyes Cotton and regenerated cellulose
benzoie acid in an aqueous medium with Z-dimethylamiriO4:6-dich1orotriazine or with 2-diethylamino-4:6-dichloro-
blue-violet‘ tints having very good fastness to solvents.
_
1
Example 7
triazine respectively.
16.4 parts’ ‘of 2-(4'-carboxyphenylamino)-4-amino-6
"Similar dyestu?s which dye cotton and regenerated cel 70 chloro-lz3zr5etriazine are converted into the correspond
iulose 'theetints shown in column III of the following
ing carboxylic acid chloride in 100 parts of nitrobenzene
table are obtained when in the above example l-aminq-
with .5 parts of thionyl chloride in the presence of 0.5
5-benzoylaminoanthraquinone is replaced by an equlpart of pyridine at 90 to 100° C. The excess thionyl
molecular amount of the starting materials listed in cOlI chloride is expelled in vacuo and 2.4 parts of lzi-diamino
um 11 of'the following table:
75 anthraquinone are added to the solution. The tempera
3,060,180
9
l0
ture is raised in the course of 1 hour to 150-155° C. and
the mixture is stirred for 3 hours at this temperature.
The yellow-brown suspension of the dyestuff of the formula
The acylating component used in this example can be
prepared in an aqueous medium by condensing the so
dium salt of 4-aminobenzoic acid with cyanuric chloride
at 0 to 5° C. in the molecular ratio of 1:1 and by fur
/N\
t IrH-OCGNH-t \‘f-m
,
N
N
\(f
11TH:
/N\
|
Ol—(|]/ IC—NH—<:>—CO—NH 0
N\ A
\C.’
NH:
is isolated by ?ltration, washed with nitrobenzene and then
ther adding one molecular proportion of the sodium
with alcohol, and dried in vacuo at 70° C.
salt of sulfanilic acid; this second condensation is per
The dyestuff dyes cotton and regenerated cellulose by 20 formed at 30-40° C. by adding sodium hydroxide solu
the method described in Example 19 orange tints having
tion dropwise at pH=6.0 to 7.5 until a solution is ob
good fastness properties. The dyeing is fast even to hot
tained and sulfanilic acid can no longer be detected.
organic solvents.
The condensation product can be precipitated from its
When in this example 2-(4'-carboxyphenylamino)-4'solution in the form of the crystalline disodium salt by
amino-6-chloro-l:3:5-triazine is replaced by an equi- 25 the addition of sodium chloride and then isolated by ?l
molecular amount of 2-(4’-carboxyphenylamino)-4-ditration.
methylamino-6-chloro-l :3z5-triazine, or of 2-(4'-carboxyExample 9
phenylamino)-4-diethylamino-6-chloro-1 :3 : S-triazine, or
‘j
~ 10.7 parts of 2:4-bis-(4’carboxyphenyl)-6-hydroxy
of 2- (3 ’-carboxyphenylamino ) -4-amino-6-chloro-l : 3 : 5
1:3:5-triazine
are slowly heated with stirring to 110° C.
triazine, dyestu?fs are obtained that have similar proper- 30
in 100 parts of nitrobenzene with the addition of 24 parts
hes‘
of thionyl chloride and 2 parts of dimethyl formamide.
Example 8
The resulting clear solution is maintained for 45 min
5.1 parts of the condensaton product from 4-aminoutes at 110° C. and then cooled, whereupon the product
benzoic acid, cyanuric chloride and sulfanilic acid of the 35 crystallizes out in the form of long, ?ne needles. It is
formula
?ltered oif, washed with dry petroleum ether and dried
N
in vacuo at room temperature.
/ \
H 0 0 C—C>—NH—-(HJN
The product of the
formula
(|3—NH—®~S 03H
01
N
\C//
4°
|
01
.
.
are converted for use as an acylatmg component mto the
/ <'1\
N/
N
C
C
I
Cl—OC-—
§ /
ll
00-01
N
corresponding carboxylic acid-sulfonic acid dichloride
with 5.0 parts of thionyl chloride and 1.0 part of di- 45 crystallizes from acetone in long, ?ne needles melting at
methyl formamide by being heated for 2 hours at 90212° C. (uncorrected).
100° C. in 100 parts of nitrobenzene. 3.0 parts of 14 parts of this acid chloride are made up at 60° C.
amino-5-benzoylamino-anthraquinone are then added,
into a clear solution in 150 parts of nitrobenzene. 6.9‘
and the whole is heated for 3 hours at 130 to 135° C. 50 parts of 1-amino-5-benzoylarnino-anthraquinone are then
After cooling to room temperature, the orange-colored
added, the whole is slowly heated to 120° C. and main
dyestuff suspension is ?ltered 01f, washed with alcohol,
tained at this temperature for 5 hours. The dyestufl of
and dried in vacuo at 70-80° C.
the ‘formula
/N\
l M05“
N\ It
I
\o/
I
The dyestulf of the probable formula
is isolated in the usual manner; it dyes cotton and re
N
(I) NH-ooONn-o/ \(|3—NH~<:>—SO2C1
l\ )1
0
61
|
||
dyes cotton and regenerated cellulose yellow tints of very
generated cellulose clear yellow tints of good fastness
good fastness to washing.
75 properties. The corresponding dyestulf from l-amino
3,060,186
11‘
i2
anthraquinone yields a greenish yellow dyeing, and the
corresponding dyestu? from 1-amino-4-benzoylaminoanthraquinone produces red tints.
is ?ltered off, washed with‘alcohol, and dried in vacuo at
90 to 1000 Q
, The analogous dyestu?- of the formula
NH_
The dyestuff dyes cotton and regenerated cellulose by
NH 0
dyes cotton and regenerated cellulose vfrom an alkaline
the method described in Example 19 greenish blue tints
hydrosul?te vat greenish blue tints of ‘good ‘fastness 20 having good fastness properties.
properties.
2:4-bis-(4'-carboxyphenyl)~6-hydroxy - 1:3:5 - triazine
Exwiwle 12
can be prepared from 2:4-'bis-(4’-tolyl)-6ihydmxy-1;3;5triazine by oxidation with potassium permanganate in an
alkaline aqumus Salution,
_
4.2 parts of aminoacedrnanthrone are acylated with
3.2 Parts Of the CaPbOXYIiC 301d chloride of 2-(4'-°'¢1Ib0XY
25 phenylamino)-4-arnino-6-chloro - 1:325 - triazine in 100
parts of nitrobenzene and 0.2 part of pyridine by being
Example 10
9.4 parts of 2-(4'-car-boxyphenylamino)-4:6-'dichloro-
stirred for 6 hours at 140 to 150° C. After cooling to
room temperature, the dyestutf of the formula
1 : 3:5-triazine are heated in 350 'parts of nitrobenzene with
O
12 parts of thionyl chloride and 1.5 parts of dimethyl 30
A
formamide for 2 hours at 110° C. The excess thionyl
chloride is distilled oif in vacuo, 10.2 parts of 4-amino
anthraquinone-Z:1(N)-acridone ‘are added at 50° ‘C., and
the whole is heated ‘for 16 hours at 80° C. and for 6 hours
at 100° C. The resulting dyestu? of the formula
01
35
l
!
_
0
N
I L smegma am.
NH
\A/
'
1
40
CO
([31
N
O
/ \
N
/0\N
NH_CO_®_NH__<|§
N%
(|;__C1
(‘l
4 is ?ltered off, washed with nitrobenzene and then with
5 alcohol, and dried in vacuo at 70° C.
The dyestu? dyes cotton and regenerated cellulose fast
brown tints_
Similar good results are obtained when in this example
is isolated in the usual manner; it dyes cotton and regenel'ated Cellulose greenish blue tints having gOOd 'PIOPeIties 0f fast?ess-
2-(4’-carboxyphenylarnino)-4-arnino-6-chloro - 113:5 - tri
Example 11
50 azine is replaced by an equimolecular amount of 2-(4'
88 parts of z_(4,_carboxyphenylamino) _ 4 _ amino _ 6_
chlor0-1:3:5-triazine are slowly heated in 350 parts of
clarbfoxyphlenylamino)-4-phenyl-6-chloro-1.3.5-tr1azine of
6 0mm 3’
nitrobenzene with 12 parts of thionyl chloride and 1.5
([31
parts of dimethyl formamide with stirring to 120° C., 55
g
whereupon the compound dissolves with evolution of hydrochloric acid.
N/ \N
After 15 minutes the excess thionyl
H
chloride is distilled off in vacuo at 70° C., 10.2 parts
|
HOO0—®‘NH_C\ //C—®
of 4-aminoanthraquinone-2:1(N)-acridone are added, and
N
the mixture is heated for 2 hours at 100° C. and for 1 60
hour at 120° C. After cooling, the blue dyestuff of the
formula
I
.
01‘ of 2'(4 -¢aTb°XYPheI1Y1alI11I10)-4-Phen0XY-6-°h10r0-1I
3 :S-triazine of the formula
or
I
u
65
NH
CO
HOOC-ONH-C \ // o—o—®
N
N
(H)
NH_O0
/C\
ll‘? 1}‘
70 The aeylating components can be prepared in crystalline
NH_C/ \C__C1
|
form by condensing in an aqueous medium equimolecular
H
amounts of the sodium salt of 4-aminobenzoic acid and a
?nely dispersed suspension of 2~phenyl-4:6-dichlorotria
O
NHZ
V
zine, or 2-phenoxy-4:6-dichlorotriazine respectively, at
75 40° C.
8,060,180
13.
14
Example 13
is prepared in an analogous manner and gives golden-'
yellow dyeings from an alkaline hydrosul?te vat.
3.2 parts of 2-(3’-carboxyphenylamino) - 4- amino-6
Example 15
chloro-1:3:5-triazine are suspended in 100 parts of dry
nitrobenzene and 2.0 parts of thionyl chloride are stirred
7 parts of 2-(4'-carboxyphenyl)-4:6-dihydroxy-123:5
in. The whole is heated to 90—100° C., and in the ’ triazine are heated in 250 parts of nitrobenzene, while
course of 2 hours a clear solution of the corresponding
being stirred, with 24 parts of thionyl chloride and 3
carboxylic acid chloride is formed. 3.45 parts of 1
parts of dimethyl formamide to 105° C. and maintained
amino-S-benzoylamino-anthraquinone are then added and
at this temperature for 2 hours. The excess thionyl
the temperature is raised to 135 to 140° C., the mixture
chloride is then distilled off in vacuo. At 80° C., 13.7
is stirredv on for 6 hours at this temperature and then 10 parts of l-aminoanthraquinone are added, and the whole
cooled to room temperature. The dyestu? of the formula
is raised to 100° C. within 30 minutes, and then heated
for 4 hours at 100° C., for 2 hours at 120° C. and for
3 hours at 140° C. The dyestutf of the formula
15
//
IiI
|
OCO-NH o
01
I]
is ?ltered off, washed with alcohol, and dried in vacuo
at 70° C.
The dyestuff dyes cotton and regenerated cellulose
very fast orange-yellow tints.
The
61
20
ll
0
o
is isolated in the usual manner; it dyes cotton and regen
erated cellulose by the method described in Example 19
or 20 clear yellow tints having good fastness properties.
The dyestu? of the formula
2-(3’-carboxyphenylamino)-4-amino - 6 - chloro
O
I
013
It
Go 0~1lu1 0
1:3:S-triazine used in this example can be prepared by
is prepared in an analogous manner; it dyes cotton and’
condensing in an aqueous medium a ?ne suspension of 2
amino-4z6-dichloro-1:3:5-triazine and the sodium salt of
3-aminobenzoic acid in the molecular ratio of 1:1 at 30
_to 40° C.
Example 14
regenerated cellulose from an alkaline hydrosul?te vat
40
gold-orange tints of good fastness properties.
Equally fast, red dyeings are obtained with the analo
gous
dyestu?
from
1-amino-4-benzoylamino - anthra
quinone, While the dyestuif from 4-arninoanthraquinone
6.1 parts of the carboxylic acid chloride of 2-(4'-car
2: 1 (N)-acridone yields greenish blue tints.
2- (4'-carboxyphenyl ) -4 : 6-dihydroxy-1 : 3 :S-triazine can
solved at 100° C. in 200 parts of nitrobenzene, 9.6 parts 45 be prepared from 2-(4’-tolyl)-4:6-dihydroxy-1:3z5-tria
zine by oxidation with potassium permanganate in an al
of l-aminoanthraquinone are added, the mixture is raised
kaline aqueous solution.
in the course of 45 minutes to 160° C. and stirred at this
temperature for 5 hours.
Example 16
The dyestu? of the formula
6.5 parts of 2-(4’-carboxyphenylamino)-4-phenyl-6
50 chloro-1:3:5-triazine in 120 parts of nitrobenzene are
heated in the presence of 4.8 parts of thionyl chloride for
1 hour at 110° C. The excess thionyl chloride is removed
boxyphenylamino)-4:6-dichloro - 1:3 :5 - triazine are dis
from the resulting clear solution by distillation under
reduced pressure. At 80° C., 4.6 parts of l-aminoanthra
55 quinone are added and the whole is maintained for 24
hours at 80° C. The dyestutf of the formula
0
II
dyes cotton and regenerated cellulose by the method
described in Example 20 yellow tints of very good fast
ness properties.
$1
'
The dyestuif of the formula
C1
5
%\
N
I
ll
ii NH-COQ
3,060,180
15 '
is isolated in the usual manner; it dyes cotton and regen-i
16‘
The dyestu? dyes cotton and regenerated cellulose very
fast blackish green tints.
When in this example aminoisodibenzanthrone is used
instead of aminodibenzanthrone, a dyestuff results which
erated cellulose by the method described in Example 19
clear yellow tints of good fastness properties.
The dyestu? of the formula
N
5 dyes cotton violet tints of similar properties.
/
o" NH-C 0C>NH-o/
i \O—O©
i.
Exam” 1e 18
\O/
2.3 parts of 4:5'-diamino-1:1'-dianthramide carbazole
A
10 are acylated with 3.2 parts of the carboxylic acid chloride
1
1
of 2-(4' - carboxyphenylamino) - 4 - amino - 6 - chloro
'
1:3:5-triazine as described in Example 7 and then isolated.
0
The dyestu? of the formula
/N\
mN-(IJ/
<HJ-HN-OOQ_NH oI
N
N
\
o
51
0
°1
NH
1
31
II
N/
\N
l
I
o NH-O oONn-cl \ % harm
N
is obtained by using in the above example 7.6 parts of
dyes cotton and regenerated cellulose brown tints having
2 - (4' - carboxyphenylamino) - 4 - phenoxy - 6 - chloro~
very good properties of fastness.
1_:3:S-triazine; it gives similar, slightly more greenish
tints.
When 2-(4'-carboxyphenylamino) - 4 ~ amino-6-chloro
1:3:5-triazine is replaced by an equimolecular amount of
Example 17
40 2 - (4’ -_carboxyphenylamino-4-phenylamino - 6 - chloro
3.2 parts of 2-(4'-carboxypheny1arnino)-4-amino-6chloro-l:3 :S-triazine are converted into the corresponding
1:3 zs'tnazule of the formula
carboxylic acid chloride in 100 parts of nitrobenzene with
_
4 parts of thionyl chloride with addition of 0.5 part of dimethyl formamide at 100 to 110° C. The excess thionyl 45
HOOC
N
/ \
NH_(1]3
(‘J-NEH
N\ /N
chloride is distilled oi the solution in vacuo, and 4.7 parts
0l
of aminodibenzanthrone are added. 0.5 part of pyridine
(III
is then added and the whole is heated With stirring for 6
hours at 140 to 150° C., and then for 3 hours at 160 to
170° C. After cooling, the dyestu? of the formula
01' 0f 2-(4'-¢arb0Xyphenylamin0)-4-cyclohexylamino-6
50 Chl0r0-1I3I5-triaZine 0f the formula
.
/N\
N
_O
v
55
N
\G//
(‘11
0
dyestuffs of similar properties are obtained.
|1
O\
These acylating components can be prepared in an
60 aqueous medium by condensing the sodium salt of 4
N/ \N
aminobenzoic acid with cyanuric chloride in the molecular
ll
ratio of 121 at 0 to 5° C. and adding one molecular pro
l
NH_O OONH~C\ /C_NH2
portion of aniline hydrochloride or of cyclohexylamine
N/
hydrochloride respectively; the second condensation is car
65 ried out at 30—40° C. and a pH value of 6.5 to 7.5 by the
dropwise addition of sodium hydroxide solution until a
primary amino group can no longer be detected. The free
carboxylic acid is then precipitated quantitatively with di
0
lute hydrochloric acid and ?ltered off.
70
Example 19
14 parts of the dyestutf obtained as described in Exam
'
ple 1 are ?nely ground in a ball mill with 126 parts of a
is ?ltered o?‘, washed with nitrobenzene and then with
neutral solution of 125 parts of dinaphthyl-methane
alcohol, and dried in vacuo at 70° C.
75 disulfonic acid in 1000 parts of water.
3,060,180
17
18
7.5 parts of the resulting paste are suspended in 250
parts of warm water. The dyestu? suspension thus ob
stirred until cold. 1 part by volume of aqueous formal
dehyde solution of 30% strength is added as preserva
tive.
tained is added to a solution heated at 50° C. of 10‘ parts
by volume of sodium hydroxide solution of 30% strength
and 6 parts of sodium hydrosul?te in 1750 parts of
water and vatted for 1 minute.
The printing paste is printed on a fabric of‘cotton or
staple ?bers of regenerated cellulose on a roller printing
machine. The fabric is dried, impregnated with a solu
tion containing per liter 24 grams of sodium hydroxide,
70 grams of sodium hydrosul-?te, 50 grams of sodium
sulfate and 20 grams of borax, squeezed to a weight in
50 parts of cotton are
dyed for 45 minutes in the dyebath prepared in this man
ner at 50 to 60° C. with addition of 60 parts of sodium
chloride. After the dyeing the cotton is washed, oxidized,
acidi?ed, again thoroughly rinsed and soaped at the boil.
An orange-yellow dyeing is obtained which has very good
10
fastness properties.
crease of 70% and ?xed for 24 seconds at 120° C. in a
Monforts reactor, thoroughly rinsed in cold water,
oxidized at 40° C., in a solution containing per liter 5
parts by volume of hydrogen peroxide of 30% strength
Example 20
and 3 parts by volume of acetic acid of 40% strength,
14 parts of the dyestu? obtained as described in Exam 15 rinsed, soaped at the boil for 15 minutes, rinsed and
dried.
ple 2 are ?nely ground in a ball mill with 126 parts of a
A clear, yellow-orange‘ print of excellent fastness
neutral solution of 125 parts of dinaphthyl-methanedi—
properties results.
sulfonic acid in 1000 parts of water. 10 parts of the
What is claimed is:
resulting paste are suspended in 100 parts of water. A
1. An anthraquinone vat dyestuif of the formula
cotton fabric is impregnated with this suspension to a 20
N
weight increase of 75% and then dried. The fabric is
then impregnated with a solution containing per liter 16
grams of sodium hydroxide, 10 to 300 grams of sodium
'
AHNOO
N
r
GONHA
chloride and 30 grams of Rongalite (trade name for sodi
um sulfoxylate formaldehyde), squeezed to a weight in 25
crease of 75%, the dyeing is steamed for 1 to 9 minutes
at 100 to 101° C., thoroughly rinsed in cold water, treat
in which. A represents anthraquinonyl.
ed with a sodium bicarbonate solution of 0.5% strength,
2. The dyestu? of the formula
rinsed, soaped for 20 minutes in a boiling 0.3% solution
3. The dyestuif of the formula
of a non-ionic detergent, rinsed and dried. A clear yel
low dyeing of good fastness properties is obtained.
Example 21
4. ‘The dyestuff of the formula
28 parts of the dyestu? obtained as described in Exam 60
ple 5 are ground in a ball mill with 112 parts of a neutral
solution of 125 parts of dinaphthyl-methanedisulfonic
acid in 1000 parts of water.
A printing paste is prepared from
100 parts of the dyestuff paste described above
65
300 parts of water
600 parts of thickening KB
1000 parts
PREPARATION OF THICKENING KD
70
(a) 20 parts of locust bean flour are strewn into 450
parts of water.
(b) 15 parts of wheat starch are pasted in 20 parts of
water and diluted with 495 parts of boiling water.
(a) and (b) are combined, boiled for 20 minutes and 75
0
mI l
I
I l
31
/ §N
if
NH-O o-O-rrn-o \
&
N
ll
0
éFNHz
3,060,180
19
>
5. The dyestu? of the formula ’ TV I
.
J
.
.
‘
V
,
_
20_
G1
i
V
N
OH NEE-COONH-é]
§N/Hl-NH E1
I
'
o
.
Goo-11m o’ '
g I1TH—-OO~C>
6. ‘The dyestu? of the formula
N
References Cited in the ?le of this patent
' UNITED STATES PATENTS
2,235,480
2,391,164
2,824,093
2,835,663
Graenacher et a1 ______ __ Mar.
Kaiser _____________ __ Dec.
Benz et a1. __________ __ Feb.
Benz _______________ __ May
18,
18,
18,
20,
1941
1945
1958
1958
OTHER REFERENCES
Bergmann: The Chemistry of Acetylene and Related
-Compounds, page 80,‘ 'Interscience Publishers Inc., New
York (1948).v
'
Hess et 21.: Nature, vol. 183, pages 260 to 261 (Jan. 24,
1959).
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