Патент USA US2127471

Patented Aug. 16, 1938
2,127,471‘
‘UNITED STATES PATENT OFFICE/
2,127,471
. AZO DYESTUFFS IN SOLUBLE IN WATER AND
' FIBER DYED THEREWI‘TH
Fritz Miiller, Willy Schumachenand Otto Scherer,
Frankfort-on-the-Main, Germany, assignors ‘to
General Aniline Works, Inc.,‘New York, N. Y.,
a corporation of Delaware
‘
.No Drawing. Application October 28, 1937. Se
rial No. 171,476. In Germany. ‘October 30,
1936
12 Claims. (01. taco-203')" .
The present invention relates to aZo-dyestuffs phuric acid ‘on- >tri?uorornethylphenylsulphides
insoluble in waterand to ?ber dyed therewith; obtainable‘ as ‘described ‘in U. S. Patent No.
more particularly, it'relates' to dyestuifs of the 2,108,606, oxidizing the nitrophenyltri?uoro
following general formula?
'
methylsulphoxides formed and reducing the
nitrated sulphone's thus obtained.
@NZNT
sbzom
/
The following examples serve to illustrate the
invention, but they are ‘not intended to limit it
thereto:
~
10
'
(l)- Grounding liquor
4 grams of 1-(2’.3’-hydroxynaphthoylamino) 10
2.4-dimethoxy-5-chlorobenzene are dissolved in
wherein the nucleus R may contain further sub
a mixture of
stituents.
We have found that‘dyestuifs of technically
valuable tints and good properties of fastness are
obtainable by coupling a diazonium compound
6 cc. of alcohol,
2 cc. of pyridine,
‘
‘
strength.
This solution is introduced
20
into a bath containing
10 cc. of Turkey red oil of 50 per cent. strength
and
10 cc. of causticsoda solution of 34° Be. in
Q-Somm
1000 cc. of water at 30° C.
or from a substitution product thereof which does
not contain any group lending solubility, with a
Developing solution
2,3-hydroxynaphthoic acid arylide.
The dyestuffs may be produced in substance,
2.46 grams of 4-methoXy-3-aminophenyl-1
tri?uoromethylsulphone are made into a paste
on the ?ber or on a substratum adapted for the
production of lakes.
15
6 cc. of water with addition of
2 cc. of a formaldehyde solution of 30 per cent.
from an amino-substitution product of tri?uoro
methylphenylsulphone corresponding with the
following formula:
_
2 c‘c.of caustic soda solution of 34° Bé. and
_
v
with
When produced on the ?ber, the dyestuffs are
subject ‘to the known high demands in respect
of resistance to alkaline agents and it is surprising
that the tri?uoromethylsulphone group present
35 in the dyestuif molecule and consisting of two’
strongly negative radicals is not only stable to
the alkaline treatment but also improves the
properties of the dyeings.
10
1.42
3.1
5
'
8
cc. of a sodium nitrite solution 1:10 are
caused to run in.
The new dyestuffs are particularly distinguished '
After
40 by their very good fastness to light.
In this re
spect they surpass the known water-insoluble azo
complete diazotization, the
Whole is ?ltered,
8
dyestuffs obtainable by coupling diazotized ami
nobenzenealkylsulphones or diazotized aminotri
20
fluoromethylbenzenes with 2.3-hydrox'ynaphthoic ’
45 acid arylides.
cc. of ‘acetone;
grams of zinc chloride,
cc. of hydrochloric acid of 20° Be. and
grams of ice are then added and, while
35
cooling,
‘
grams of dissolved sodium acetate are
added and after addition of
grams of‘sodium chloride the whole is
40
made up} to
‘
1000
cc. by means of water.
The aminophenyltrifluoromethylsulphones used
in this process as diazo-components may be pre
Dyeing process
pared by reductionofthe tri?uoromethylphenyl
50 grams ‘of cotton are treatedfor half an hour
at 30° C. in the grounding liquor. The whole is
606; ‘issued February 15, 1938, or by reduction’ then well centrifuged and dyed for half an hour 50'
of the nitro-compounds made by nitration‘ ‘of ‘ in the developing solution; the material is sub
sulphones substituted by a nitro-group and ob—.
tainable as described in U. S. Patent ‘No. 2,108,
tri?uoromethylphenylsulphones. The ortho-‘ and sequently rinsed, soaped at boiling temperature,
para-aminoederivatives are suitably prepared by rinsed again and dried. A yellowish red dyeing
causing nitric acid to act in the presence of sulé‘ of very good fastness to light is obtained. The
2
2,127,471
dyestu? corresponds with the following formula:
00113
802C173
no) -benzene
20 grams of Turkey red oil, and
20 cc.
of caustic soda solution of 32.5
per cent. strength and made up to 1 litre and is
then dried. Thereupon, the fabric is printed with
a printing paste prepared as follows: The solid 10
OCHa
\
\CONHO—OOHa
10
(3) A cotton fabric is padded with a solution
containing
13.2 grams of 1-(2’,3’-hydroxynaphthoylami
diazonium compound from
12.7 grams of 4-methoxy- 3 -aminophenyl-1
tri?uoromethylsulphone is dis
(2) While well stirring, a solution of 29.5 parts
by weight of 1-(2’.3'-hydroxynaphthoylamino)
2-methoxybenzene rendered alkaline by means
ed the amount of sodium acetate solution neces
sary for binding the excess of mineral acid, is
caused to run slowly into a diazo-solution pre
pared in the usual manner from 22.5 parts by
20
solved in
of acetic acid of 50 per cent.
10
cc.
400
cc.
400
grams of starch tragacanth thickening
15 of caustic soda and to which there has been add
strength and
of water; the Whole is thickened
by means of
weight of B-aminophenyl-l-tri?uoromethylsul
phone. After formation of the dyestuff is ?n
ished, the whole is ,?ltered with suction and
washed well. The dyestuff is advantageously
and made up to
1
litre.
After printing, the fabric is dried, then treat
worked up into the form of a paste. When mixed
with one of the usual substrata, it yields an
ed with a hot sodium carbonate solution (10
grams per litre) , rinsed while cold, soaped at boil 25
orange-red lake having very good properties of
fastness. The dyestuff may also be prepared by
up. A print having a vivid red tint is obtained.
mixing the diazo solution with a substratum, for
instance, barytes, zinc White or the like, and run
30 ning in the arylide solution.
ing temperature, rinsed again, dried and Worked
The following table includes a number of other
azo-dyestuffs obtainable according to the pres
ent invention:
Diazo-compound irom—
30
Coupled with—
Tint
1-(2’,3’-hydroxynaphthoylamina)
35
35
(l) 4~methoxy-3-aminophenyl-l-tri?uoromethylsulphone ____ __ 2-methyl-i-methoxybenezene.___ Yellowish red.
(2) 4-Inethoxy‘3-aminophenyl-l-tri?uoromethy1sl1lph0ne
3methyl-truethoxybenzene. ..
(3) 4-n1ethoxy-3-aminophenyl-l-tri?uoromethylsulphone_
4-methoxybenzene
(5) 4 methoxy 3 aminophenyl
Benzene _ _ _
‘
Vivid middle-red.
_ _
__
_ _
D0.
(7) 4-methoxy-3-armnophenyl-1-tr1?uoromethylsulphone
2-methoxy-S-chlorobenzene ____ __ Scarlet.‘
(9) 4-inethoxy-3-aminophenyl-l-tri?uoromethylsulphone__
2-ethoxybenzene _____________ __
(8) 4-methoxy-3-arninophenyl~l-tri?uoromethylsulphone
40
2, 5-d1methoxy-‘i-chlorobenzene.. Yellowzsh red.
0) 4-methoxy-3»aminophenyl~l-tri?uoromethylsulphone.
45
Scarlet.
Yellowish red.
_ _ __
2-methyl
40
Do.
2-i'nethoxybenzene ______ __
(4) 4-methoxy-3-aniinophenyl-l-tri?uoromethylsulphone
Naphthalene__
carlet.
____ .. V1vid bluish red.
(11) 4-meth0xy-3-aminophenyl~1-tri?uoromethylsulphone_
4-chl0robenzen
(12) 4-ethoxy-3-aminophenyl-l-tri?uoromethylsulphone_
Benzene_-_._..
(13) 3-aminophenyl-l-tri?uoromethylsulphone ______ __
2, 4-dimethoxy
___.
(l4) 3-aminophenyl-l-tri?uoromethylsulphone ________ __
Z-methoxybenzene ___________ __
___
_ Do.
____ __
Middle-red.
lorobenzene," Brown-red.
(l5) é-methyl-B-aminophenyl-l-triliuoromethylsulphone___ ._ 2-rnethoxybenzene.
_
(l6) 4-methyl-3-aminophenyl-l-tri?uoromethylsulphone _____ __ 3-rnethyl-4-methoxybenzen
Red-orange.
Vivid red-orange.
Brick-red.
(l7) 4-ch1oro-3-aminophenyl-l-tri?uorornethylsulphone..r____. 2-methoxybenzene ___
Orange.
(18)
(l9)
(20)
(21)
Red-orange.
D0.
Orange.
Yellow-red.
4Achlor0-3-aminopheny1-l-tri?uoromethylsulphone ______ __ Z-methylbenzene
4-chloro-3-aminophenyl-l-tri?noromethylsulplione ______ _. 4-cl1lor0benzene-
4-bromo-3-aininophenyl-l-tri?uoromethylsulphone _____ _. 2-methoxybenzene
5-chl0ro-2-aminopheny1-l-triiiuoromethylsulphone ______ __ 3-methyl-4-methoxybenzene_
(22) 5-chlor0-2-aminophenyl-l-tri?uoromethylsulphone ______ __
(23) 4-aminophenyl-l-triiluoroniethylsulphone ______ __
__
4-chlor0benzene..Z-methoxybenzene
_
(24) 4-aminophenyl-1-tri?uoromethylsulphone ______________ __ 4-methoxybenzene
(25)h3-aminophenyl-4-methylsulphone- l-tri?uoromethylsul-
Yellowish scarlet.
Scarlet.
Brownish red.
Benzene. _ _
Golden-yellow.
1) one.
(26)
3-arninophenyl-lieethylsulphone-1-tri?uoromethy1su_lphone.
(27) 4-methoxy-3-aminophonyl-l-tritluoromethylsulphone______
(28) 4-methyl-2-aminophenyl-l-tri?noromethyl nlnhrme
Benzene _ n .
__
_ _ _ _ _ _ . _ __
Naphthalene ___________________ __
Nnnhihalene
Do.
Yellowish scarlet.
Vivid scarlet.
1-(2’, 3’-hydrozynaphthoylamino)
(29) imethyl-2-aminophenyl-1~tri?uoromethylsulphone.__
(30) 2-chloro-5-arninophenyl-l-tri?uoromethylsulohone
g,, 4-dich1oro-G-aminophenyl-1-tri?u0romethylsulphon
4-dichloro-6-aminophenyl-letri?uoromethylsulphone
(33) 3, 4-dichloro-5-aminophenyl-1-tri?uoroinethylsulphon
_
60
2-rnethyl-4ech1orobenzene ______ _.
Berwone
__
z-methoxybenzene ________ __
2-methyl-4-chlorobcnzene.
_-
___
_
li-chlorobenzene _______________ __
Yellowish scarlet.
Scarlet.
Covered red.
Bluish red.
Vivid red-orange.
65
2-2’, 3'-hydrozy'naphthoylamino)
(34) 3, 4-dichloro-G-aminophenyl-l-tri?uoromethylsulphone___ Naphthalene ___________________ -_ Scarlet.
70
70
1-(2’, 3’-hydrozymphthoylamino)
(35) 2,4-dibromo-6-aminophenyl-l-trl?uoromethylsulphone-__ Z-methoxybenzene _____________ __ Red.
(36) 2,4-dimethoxy-5-aminophenyl-l-tri?uoromethylsulphone 2'methyl-4-chlorobenzene ______ __ Ruby-red.
(37) 2, 4-dimethoxy-5-aminophenyl-l-tn?uoromethylsulphone 2, 4-dimethoxy-5-chlorobenzene._
(38) 2, 4-diethoxy-5-aminophenyl-l-tri?uoromethylsulphone___ 2-4-dimethoxy-5-chlorobenzene__
75.
Do.
Do.
(39) 2, 5-d1ohloro4-aminophenyl-l-tritluoromethylsulphone__. 3-nitrobenzene ________________ _; Brick-red.
75
2,127,471
Since an object of the present invention is to
provide dyestu?s of good fastness properties
which dyestuffs are insoluble in water and a1
kalies, it is to be understod that the aromatic
nuclei of the general formulae appearing in the
appended claims do not contain any substituents
which are known to render organic compounds
soluble in water or alkalies and‘to tend to de
preciate the fastness of the dyestuifs to alkalies.
10 Substituents of this kind are, for instance, the
sulphonic and the carboxylic acid group.
We claim:
1. The water-insoluble azo-dyestuffs of the fol
15
lowing general formula:
X2
X1>< lI
\m
3
ries, yielding, when produced on the ?ber, scarlet
to red shades of good fastness properties, particu
larly of very good fastness to light.
‘
4. The water-insoluble azo-dyestuff of the fol
lowing formula:
/
OCHs
SOzOFa
1O
.
yielding, when produced on the ?ber, yellowish
red shades. of good fastness properties, particu
N=N~
l
larly of very good fastness to light.
,
5. The water-insoluble azo-dyestu?" ‘of the fol
lowing formula:
SOzCFa
20
OCH3
\QONELR
20
wherein X1 stands .for a member of the group
consisting of hydrogen, halogen and alkoxy, X2
25 for a member of the group consisting of hydro
CH3
gen, halogen, methyl, alkoxy and alkylsulphonyl,
and R means a member of the group consisting
of radicals of the benzene and naphthalene se
ries, yielding, when produced on the ?ber, golden
30 yellow to ruby-red shades of good fastness prop
erties, particularly of very good fastness to light.
2. The water insoluble azo-dyestuifs of the
following general formula:
\c ONE-O
yielding, when produced on the ?ber, vivid mid
dle-red shades of good fastness properties, par
ticularly of very good fastness to light.
6. The water-insoluble azo-dyestuff of the fol
lowing formula:
OCH:
35
35
scion
/
40
OH
\OONELR
wherein X stands for a member of the group
consisting of hydrogen, halogen, methyl, alkoxy
and alkylsulphonyl, and R means a member of
45 the group consisting of radicals of the benzene
and. naphthalene series, yielding, when produced
on the ?ber, golden-yellow to red shades of good
fastness properties, particularly of very good
fastness to light.
3. The water-insoluble azo-dyestu?s of the fol
lowing general formula:
0 .alkyl
pee.
OzCFs
/
OH
\OONH.R
60 wherein R. means a radical of the benzene se
SOzOFa
\o ONE-Q01
40
yielding, when produced on the ?ber, vivid bluish
red shades of good fastness properties, particu
larly of very good fastness to light.
'7. Fiber dyed with the dyestu?s as claimed in 45
claim 1.
8. Fiber dyed with the dyestuffs as claimed in
claim 2.
9. Fiber dyed with the dyestuffs as claimed in
claim 3.
50
10. Fiber dyed with the dyestu? as claimed in
claim 4.
11. Fiber dyed with the dyestu?‘ as claimed in
claim 5.
12. Fiber dyed with the dyestuff as claimed 55
in claim 6.
FRITZ SCHUMACHER.
WILLY
OTTO SCHERER.
60