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Патент USA US3073834

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United states
EQQ
3,073,824
Patented Jan. 15, 1953
1
2
3,073,824
groups and halogen atoms, and also sulfone groups and
substituted su'lionarnide groups.
The acylatable amino group bound to R2 is preferably
in meta- or para-position to the nitrogen bridge.
DYESTUFFS CONTAINING NITRO AND ANTHRA
QUINONE CHROMOPHORES AND A CHLORO
TRIAZINE MOIETY
As examples of such o-nitrodiaryl-amino compounds
Raymond Gunst, Binningen, and Hans Wilhelm Liechti,
Oberwil, Switzerland, assignors to Ciba Corporation, a
the following may be mentioned:
4'-amino-2-nitrodiphenylamine-ll-sulfonic acid,
4'-arnino-2-nitrodiphenylamine-3':4-disulfonic acid,
corporation of Delaware
No Drawing. Filed Feb. 9, 1961, Ser. No. 88,016
Claims priority, application Switzerland Mar. 4, 1959
3'-amino-2'-methyl-2-nitrodiphenylamine-?l':4 - disulfonic
4 Claims. (Cl. 260-249)
acid,
4'-amino-3'-carboxy-2 - nitrodiphenylamine - 4 - sulfonic
The present application is a continuation-in-part of
our copending application Serial No. 8,482, ?led Febru
ary 15, 1960 (now abandoned).
acid,
3'-amino-2’-methy1-2:4 - dinitrodiphenylamine - 4’ - sul
' The present invention relates to new anthraquinone
dyestuffs which contain both nitro and anthraquinone 15
chromophores and which, like for example the dyestutf
of the formula
‘fonic acid,
4’-amino-2-nitro-4 - carboxydiphenylamine - 3' - sulfonic
acid,
3'-amino-2-nitrodyphenylamine-2':4-disulfonic acid,
I
N
O2N
3'-amino-4'-methyl~2 - nitrodiphenylamine - 2':4 - disul
correspond to the general formula
30
fonic acid.
As anthraquinone dyestuffs of the type described there
come into consideration as starting materials for the
present process those which contain an acylatable amino
group bound to the benzene nucleus R, particularly an
NH2-group; this amino group can be in meta-position to
the —NH-group, or preferably in para-position, and the
benzene nucleus can contain further substituents, such as
alkyl groups or particularly an -—SO3H-group.
in which R stands for a benzene radical, X and Y each
represent a nitrogen bridge and B the radical of an
o-nit-rodiarylarnine which contains at least one sulfonic
acid and/ or one carboxylic acid group.
As examples of such anthraquinone dyestuffs which can
be used as starting materials in the present process there
may be mentioned:
To prepare these dyestu?s a trihalogen-l :3 :S-triazine,
especially cynauric chloride, can be condensed in any
order of succession on the one hand with an o-nitrodiaryl
45
amine which contains at least one sulfonic acid and/or
one carboxylic acid group and at least one acylatable
amino group, and on the other hand with an anthra
quinone dyestu? on the formula
(3)
thraquinone-Z-sulfonic acid,
1-amino-4-(4’-amino-3' - methylphenylamino) - anthra
quinone-Z-sulfonic acid,
50 1-amino-4-(3’-arnino-4’:6' - dimethylphenylamino) - an
E NH:
/
1-amino-4-(4’- or 3'-aminophenylamino)—anthraquinone
2-sulfonic acid,
1-amino-4-(3’~amino-4'- or -6'-methylphenylamino)-an
thraquinone-2-sulfonic acid,
1-amino-4-(4’-aminophenylamino) - anthraquinone - 3'
son
sulfonic acid diethylamide-Z-sulfonic acid,
0/
(H) NH-R
l-amino-4-(4’-aminophenylamino) - anth‘raquinone - 3'
55
disulfonic acid,
in which R stands for a benzene radical which contains
1-amino-4-(4’-aminophenylamino)eanthraquinone - 2:5-,
an acylatable amino group, so that the resulting dyestu?
-2:6-, -2:7- or -2:8-disulfonic acid,
condensation products contain a single reactive halogen
1-arnino-4-(3'-aminophenylamino)-anthraquinone - 2:4’
atom.
disulfonic acid,
As o-nitrodiarylamines of the type described there
'
1~arnino-4-(5'-amino-2' - methylpheny’lamino) - anthra
come into consideration as starting materials for the
quinone-2:4’-disulfonic acid.
present process preferably o-nitrodiphenylamines of the
formula
methyl-sulfone-Z-sulfonic acid, and
1-amino-4-(4’-aminophenylarnino)-anthraquinone - 2:3’
65
The condensations according to the present invention
may be carried out in any order of succession.
All the condensations are advantageously carried out
in which R1 and R2 each represent a benzene radical and
in
an aqueous medium at a pH valued between 6 and 8.
the two radicals R1 and R2 together contain at least one
sulfonic acid and/ or one carboxylic acid group.
70 Depending on the choice of starting materials it can be
an advantage to raise the pH value somewhat from step
The benzene radicals R1 and R2 may contain further
substituents, such as for example alkyl groups, alkoxy
to step. As a rule it is advisable to keep the pH valued
3,073,824
4
To obtain products with similar properties the follow
as constant as possible at the separate steps, which is
possible by checking continually and neutralizing the
ing components are used:
hydrohalic acid liberated, for example by means of an
alkali metal carbonate or alkali metal hydroxide.
The dyestuffs obtained by the present process are new.
They are valuable dyestuffs which are suitable for dyeing
and printing a wide variety of materials of ?brous struc
ture, such as wool, silk, regenerated cellulose, such as
viscose, linen or especially cotton. They are suitable
Diphenylarnlne
Derivative
Anthraquinone
Derivative
Tint on
Cotton
1___ 3’-amino~2'nitrodiphen- 4-(3’-amino~4’-su1tophen- Grey.
ylamine43’A-disulionlc
ylarnlno)-l-aminoan~
acid.
thrgquinone-‘lasulfonie
for dyeing by the so-called direct dyeing method and 10
particularly for printing and the pad steam process by
2.-- 4’-amlno-2-nitrodlphen- 4-(4’-amlno3'-sulfophen-
which the dyestuffs are applied to the material to be
3___ 4’-amino-2-nltrodlphen- 4-(3’-amino-4’-sullophen~ Greenish
ylaminc-é-sulfonic
ylamino)-1-arninoangrey.
ylamine-é-sulfanilide-
ylamino)-l-aminoan—
3':4”—disulionic acid.
thfgquinone-Zsuifonic
ac
dyed and then ?xed, for example to cellulose ?bers, by
means of an acid-binding agent.
The dycings obtained with the new dyestuifs on cellu~ 15
losic ?bers are, as a rule, distinguished by a good fast
ness to light and especially by an excellent fastness to
acid.
.
thrgquinone-Qsulionic
801
4.- _ 4’-amino-2-nitr0diphen'
ylamine-3'z4-disultonic
acid.
Olive green.
.
4-(4’-am1no~3’-sul1’ophen-
ylamino)-1-aminoan
Olive green.
thraquinone-Z-sulionic
acid.
washing.
The following examples illustrate the invention, the
parts and percentages being by weight unless otherwise
stated.
Example 1
Example 4
18.6 parts of cyanuric chloride are ?nely suspended in
300 parts of ice and 200 parts of ice-water. There is
then added a solution, adjusted to pH 7.5, of 35.3 parts
of 4'-amin0~3'-sulfo-2-nitrodiphenylamino - 4 - carboxylic
18.6 parts of ?nely divided cyanuric chloride are sus
pended in 300 parts of ice and 200 parts of ice-water. 25 acid in 500 parts of water. The temperature is advanta
geously kept between 5 and 10° C., and the pH between
A solution of 30.9 parts of 4'-amino-2-nitrodiphenyl
6
and 6.5. After 30 minutes, the condensation is ?nished.
amine-4-sulfonic acid in 500 parts of water adjusted to
A solution, adjusted to pH 7.5, of 48.9 parts of 4-(4'
pH 7.5 is added. The temperature is advantageously
amino-3'-sulfophenylamino) - 1 - aminoanthraquinonc-Z
maintained between 5 and 10° C., the pH value between
sulfonic acid in 500 parts of water is added and the
30
8 and 6. After 30 minutes, condensation is complete.
whole is stirred for 24 hours at 40-45 ‘’ C. and at a pH
A solution of 48.9 parts of 4-(4’-amino-3'-sulfophenyi
of 6—6.5. An addition of sodium chloride precipitates
amino)-l-aminoanthraquinone-Z-sulfonic acid in 500
the
condensation product, which is then ?ltered off and
parts of water adjusted to pH 7.5 is added to the re
action mixture and the whole is stirred for 14 hours at M dried. In the pad-dyeing method, the new dyestu? dyes
40 to 45° C. and at a pH value of 6.5 to 7.5. On the U! cellulose ?bers olive green shades that are fast to washing
and light.
addition of sodium chloride the dicondensation product
When instead of the 4'-amino-3'-sulfo-2—nitrodiphcnyl
is precipitated, ?ltered and dried. The new dyestu?f dyes
amine-4-carboxylic acid the isomeric 4’-amino-4-sulfo-2
cellulose ?bers bluish olive tints which are fast to wash
nitrodiphenylamine-3'-carboxylic acid is used, a dyestutf
ing and light by the method described in Example 4.
40 with similar properties is obtained.
Example 5
Example 2
18.6 parts of cyanuric chloride are suspended in 300
18.6 parts of ?nely divided cyanuric chloride are sus~
parts of ice and 200 parts of ice-water. There is added
pended in 300 parts of ice and 200 parts of ice-water.
a solution, adjusted to pH 7.5, of 35.3 parts of 4’-amin0—
A solution of 48.9 parts of 4-(4'-amino-3’-sulfophenyl 45 3’~sulfo-2-nitro-diphenylamine-4-carboxylic
acid in 500
amino)-l-amino-anthraquinone-Z-sulfonic acid in 500
parts of water. The temperature is advantageously kept
parts of water adjusted to pH 7.5 is added. The tem~
between 5 and 10° C., and the pH between 6.5 and 6.
perature is maintained between 0 and 5° C. and the pH
After 30 minutes the condensation is ?nished. A solu
value from 5 to 7. After 30 minutes, condensation is
tion, adjusted to pH 7.5 of 48.9 parts of 4-(3’-amino-4
50
complete. A solution of 38.9 parts of 3'-amino-2-nitro
sulfophenylamino) - l - aminoanthraquinone-Z-sulfonic
diphenylamine-6’:4-disulfonic acid in 500 parts of water
acid in 500 parts of water is added and the whole is
adjusted to pH 7.5 is added to the reaction mixture.
stirred for 24 hours at 40—45° C. and at a pH of 6 to 6.5.
The whole is stirred for 48 hours at 40 to 45° C. and at
An addition of sodium chloride precipitates the condensa
a pH value of 5 to 7. On the addition of sodium chloride
tion product, which is ?ltered and dried. In the pad-dye
the dyestulf is precipitated, ?ltered and dried. The new 55 ing and exhaust processes the new dyestulf dyes cellulose
dyestu?' dyes cellulose ?bers pure greenish blue tints.
?bers greenish gray shades which are fast to light and
Example 3
washing.
When instead of the 4'-amino-3’-sulfo-2-nitrodiphenyl
amine-4-carboxylic
acid used in Example 5 the isomeric
18.6 parts of ?nely divided cyanuric chloride are sus 60 4'-amino-4-sulfo-2-nitrodiphenylamine-3’-carboxylic
acid
pended in 300 parts of ice and 200 parts of ice-water.
is
used,
a
dyestutt
with
similar
properties
is
obtained.
A solution of 38.9 parts of 4’-amino-2-nitrodiphenyl
amine-3'z4-disulfonic acid in 500 parts of water adjusted
Example 6
to pH 7.5 is added. The temperature is preferably main
2 parts of the dyestutf obtained as described in Example
tained between 5 and 10° C., the pH value between 8 and 05
1 are dissolved in 100 parts of water. A spun rayon
6. After 30 minutes, condensation is complete. A solu—
fabric is impregnated with the resulting solution so that
tion of 48.9 parts of 4-(3'-amino-4'-sulfophenylamino)
its weight is increased by 75%, and then dried.
1-aminoanthraquinone-2-sulfonic acid in 500 parts of
water adjusted to pH 7.5 is added and the whole is stirred
for 48 hours at 40 to 45° C. and at a pH value of 5 to
6.5. The dyestuff is obtained as a powder by evaporat
ing the reaction mixture at 50° C. under reduced pres
sure. The new dyestu? dyes cellulose ?bers greenish
grey tints by the method described in Example 4.
The fabric is then impregnated with a solution heated
70 to 20° C. which contains per liter 10 grams of sodium
hydroxide and 300 grams of sodium chloride; the fabric
is then squeezed to a weight increase of 75%, steamed
for 60 seconds at 100 to 101° C., rinsed, soaped for a
quarter of an hour in a boiling solution of a non-ionic
75 detergent of 0.3% strength, rinsed and dried.
3,073,824
5
6
An olive green dyeing fast to washing and light is
01
obtained.
If a cotton fabric is used instead of the spun rayon
fabric a similarly good result is obtained.
What is claimed is:
%
N
5
/C
£_NH_
NO,
\N /
NE:
NH
SOaH
soul
01
C
\N
_HN_A;
1. Anthraquinone dyestu? of the formula
(I?
&
H
'
'
10
(I;
3. Anthraquinone dyestu?’ of the formula
N/ \ N
H
NH:
wherein R1 is phenylene and the --NH-- groups of
NH
—-NH--R1-—NH—- are in one of the relationships meta
and para with respect to each other, and R2 is o-nitro- 20
phenyl, R1 being further substituted by a member selected
from the group consisting of sulfo and carboxy in a posi
tion para to —NH—, and R2 being further substituted by
a member selected from the group consisting of sulfo and
carboxy in a position meta to —-NH——.
X
in which one X is __SO3H and the other X is of the
formula
25
O1
2. Anthraquinone dyestu? of the formula
00
NH:
1
/
H
N/ \N
SOaH
'
‘I
--HN--o§
/O—NH
N
30
N 0|
\OO/
NH
X
H038
x
NH
35
in which one X is SO3H and the other X is of the formula
soaH
4. The dyestu? of the formula
NH:
00
/
S0311
01
00’
|
NH-
so H
:
\
Ilq/ \N
so 11
SO H
a _
a
NIL-d\ /J)—NH
N
NH
OzN-
No references cited.
SOi-NH
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