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Патент USA US3098074

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United States Patent 0
1CC
3,098,064
Patented July 16, 1963
1
2
3,09%,064
cases it is advisable to carry out the diazotization with the
use of organic solvents soluble in water such, for example
WATER-SOLUBLE DISAZO DYES CONTAINING
TWO THIOSULFURIC ACID GROUPS
as acetone. The diazonium salts of aryl-thiosulfuric acids
obtained in this manner frequently crystallize as hybrid
ions in the form of interior salts.
Depending on their constitution the diazotized amino
aryl-thiosulfuric acids are reacted with compounds ca
Werner Schultheis, Konigstein, Taunus, Kurt Schimmel
Schmidt, Frankfurt am Main, Hermann Hoffmann,
Bad Soden, Taunus, and Edwin Baier, Frankfurt am
Main, Germany, assignors to Farbwerke Hoechst
Aktiengesellschaft vormals Meister Lucius & Briining,
Frankfurt am Main, Germany, a corporation of Ger
pable of being coupled in an acid, neutral or alkaline
solution, and the azo-dyestu?s thus obtained which are
easily soluble in water are isolated by the addition of
salt.
The water-soluble azo-dyestu?'s obtained by the process
of the present invention which contain, for example, 1
many
No Drawing. Filed Apr. 18, 1960, Ser. No. 22,718
Claims priority, application Germany Apr. 24, 1959
6 Claims. (Cl. 260-176)
The present invention relates to new water-soluble azo
to 4 thiosulfuric acid groups in the molecule are advan
dyestnt‘fs containing one or more thiosulfuric acid groups 15 tageously prepared in the form of their well 'crystallizing
and to a process for preparing them; more particularly it
relates to dyestuifs of the following general formula
alkali metal or ammonium salts, since the dyestuffs con
taining free thiosulfuric acid groups tend to instability
unless they are obtained as inner salts. The dyestuffs are
suitable for dyeing and printing wool, silk, leather, poly
20 amides or polyurethanes from an acid bath and yield
yellow, orange, red, brown, blue and green dyeings which
mostly possess good properties of fastness.
The following serve to illustrate the invention but they
are not intended to limit it thereto, the parts being by
25
weight unless otherwise stated, and the relationship of
parts by Weight to parts by volume being the same as
that of the kilogram to the liter:
A solution of 18.7 parts of 3-amino-benZene-sulfonyl
amino-?-ethyl-thiosulfuric acid and 6 parts of sodium bi
30 carbonate in 100 parts by volume of water to which 4.4
parts of sodium nitrite have been added, is run at 0° C.
into a mixture of 24 parts by volume of concentrated by
drochioric acid and 100 parts by volume of water. The
in which one X on each of the benzene rings stands for
hydrogen and the other X for hydrogen, methyl, methoxy
or chlorine, one Y stands for hydrogen or methoxy and
suspension of the diazonium salt thus prepared is adjusted
the other Y stands for hydrogen, methyl, methoxy or chlo 35 to a pH value of 5 to 6‘ by means of sodium bicarbonate.
rine, and Me represents an alkali metal or ammonium.
We have found that aromatic amines containing one or
Into this suspension is then run a solution of 10 parts
1,4 - di-(acetoacetylamino)-2-chloro~5-methoxybenzene in
50 parts by volume of water and 5 parts by volume of a
more thiosulfuric acid groups bound to the aromatic nu
cleus, via bridge members interrupted by hetero atoms,
sodium hydroxide solution of 33% strength. The mix
can be diazotized and reacted with compounds capable of 40 ture is brought into a stirrable state by the addition of
being coupled to obtain azo-dyestulfs soluble in water.
acetone and heated to 60° C. whereby the dyestuif formed
It was 'known that compounds containing thiosulfuric
is obtained in crystalline form. It is ?ltered oif and dried
acid groups are converted into disul?des by oxidizing
at 60° C. The dyestuff dyes wool fast greenish yellow
agents such, for example, as iodine. Since nitrous acid
tints.
liberates iodine from iodides, it could be assumed that 45
The dyestuffs listed in the following table were prepared
nitrous acid forms also disul?des when acting on com- " in like manner. They yield on natural protein ?bers, such
pounds containing thiosulfuric acid groups. The more
as wool and silk, and on polyamide and polyurethane
surprising is the observation that aromatic amines con
?bers dyeings which possess a very good fastness to wet
taining thiosulfuric acid groups can be diazotized without
processing.
dii?culty and without the formation of disul?des. The 50
only exception are the ortho-amino-aryl-thiosulfuric acids
and the substitution products thereof, since these com
Diazo Component
Coupling Component
Tint
pounds are converted during the diazotization into non
coupling ortho-arylene-diazo-sul?des (German Patent
120,540). The para-amino-phenylthiosulfuric acid obtain
3 - amino - benzyl - thiosulfuric
55
able according to German Patent 120,540 is said to be
diazotiz'able but actually yields the 4,4'-diamino-diphenyl
acid.
4 ' amino - benzene - sulfonyl -
Chem. Soc. London, 1930, 2691).
3-amino-benzene-sulionyl-
in admixture with alkali nitrite into an acid.
In some
greenish
yellow.
reddish
yellow.
rio acid.
3 - amino - 6 - chloro -benzeue sulionyl - amino - 1S - ethyl -
Such amino-aryl-thiosulfuric acids that are di?icultly solu
ble in water, can be indirectly diazotized by introducing
them in the form of their easily soluble alkali metal salts 65
benzene.
amino - B - ethyl - thiosulfu -
disul?de which is diazotizable as could be expected (J.
Due to the sensitivity of the thiosulfuric acid groups, 60
the amino-aryl-thiosulfuric acids are diazotized in the cold,
preferably at a temperature ranging from 0° C. to +5” C.
1,4 - di- (aeetoaeetylamino) _-___do ____________________ __
_____do ____________________ __
Do.
_____do _____________________ -_
greenish
thiosulfuric aeid.
(methylamino)-?-ethyl-
yellow.
thiosulfuric acid.
4-amino-benzoylamino-B-
.____do _____________________ _. golden
3-amino-benzenesulfonyl-
.____do _____________________ __
ethylsthiosulfurlc acid.
yellow.
amilno-?-ethyl-thiosulfurie
ac1
reddish
yellow.
.
D0 ______________________ __ 1,4-di-(acetoacetylamino)-
2-chloro-5~methoxy
benzene.
greenish
yellow.
3,098,064
3. A dyestuff of the formula
Diazo Component
Coupling Component
Tint
OH1-—CO-—CH—N=N-—
B-amino-benzyl-thiosuliuric
acid.
1,4-di-(acetoacetylamino)2-chl0ro-5-methoxy
golden
yellow.
(I) 0
5
|
benzene.
3-amino-G-methyl-benzene-
sulfonylamino-?-ethyl-
—S O z-NH——CH2—-C H2—S——S O aNa
01130
NH
_____do _____________________ ._ greenish
|
yellow.
thiosuliuric acid.
—0 CH3
3-amino-4-metl1oxy-benzene-
sulfonylamino-?-ethyl-
_____do _____________________ __
golden
yellow.
thiosulfuric acid.
3-amino-benzene-sulionyl-
__-,_do _____________________ .. greenish
(cyano-ethyl-amino)-B4-arnino-benzoylamino-Bethyl-thiosulfuric acid.
1,4-di-(aeetoacctylamino)-
ethyl-thiosulfuric acid.
yellow.
Do.
1O
1
|
NH
2-chloro-benzene.
3-amino-4-methoxy-benzene-
C0
____.do _____________________ __
Do.
]
sulfonylarnlnot?-e’thylthiosuliurie acid.
O H3—CO-— O H—N=N——
-S O n—NI-I- 0 H2— C Hz-S—S O aNn
15
Do ______________________ .. 2,5-di-(acetoacetylamino)-
toluene.
3-amino-benzene-sulionyl-
(methylamino)-B-ethyl
thiosulfuric acid.
3-amino-benzene-sulionylamino~?-ethyl-thiosuliurie-
golden
yellow
_____do _____________________ ._
yellow.
__-__do _____________________ -_
golden
C1130
4. A dyestuif Of the formula
acid.
yellow
Do ______________________ __ 2,5-di-(acetoacetylamino)-
20
CH3—CO—CH--N=N—
Do.
3-amino-4-methoxy-benzene-
sulionylamino-?-ctliyl-thlo-
-—SO2—NH—CH2—CH2—S—-SO3N8
|
anisol.
O0
.-___do _____________________ __
Do.
I
_____do _____________________ _.
yellow.
01130-
NH
sulfuric acid.
3~amino-benzene-sulfonyl-
(methylamino)-B-ethyl-
25
thiosuliuric acid.
3-amino-4-methoxy-bcnzenesulionylamino-?‘ethylthiosuliurlc acid.
2,5-di~(acetoacetylamino)-
hydroquinone-dimethyl
—0 Ha
golden
orange.
ether.
3-amino-benzene-sulfonyl-
_____do _____________________ __
Do.
|
amino-?-ethyl-thiosuliuric acid.
NH
[
CH30—
30
_
(I10
CH3—CO—-CH—N=N—
—SO2—NE—CH2—CH2—S—SO3N3
We claim:
1. Water-soluble disazo-dyestuffs of the formula
CHa——CO—(!3H—N=N—
CO
1
X——
5. A dyestu? of the formula
-—SO1-—NH—CHz—CHi—SSO3Me
35 CH3—CO—(‘3H-—N=N—
—SO2—NH—CHz-CH2—S—SO:N&
CO
—X
|
NE
NH
—Y
40
Y
——OOH3
CHgO
I|\IH
IH
N _
l
X-
(I? 0
CH3—CO—OH—N=N—
—X
45
—SOa——NH—-CH2—CHz—-SSO;1\I8
|
CO
I
cH,_C0_c1-1_N=N_.
_s02__N11_CH2__0H,_s_so,Na
wherein one X on each of the benzene nuclei stands for
hydrogen and the other X for a member of the group 50
6' The dy?stll? of 1116 fofmul?i
H
consisting of hydrogen, methyl, methoxy and chlorine,
CHH—CO-C-N=N—
one Y stands for a member of the group consisting of
hydrogen and methoxy and the other Y for a member
.
I
.
NH
of the group consisting of hydrogen, methyl, methoxy and
chlorine,
and Me
represents a member
of the group con
.
.
.
.
sisting of alkali metals and ammonium.
1
55
2. A dyestuif of the formula
CH;—CO-—OH—N=N
o
—SOZ—NII—CH1—OHQ—SSOZNB
()0
_o1
OH3_O_
—SOz—NH—CH2——GH1—-S—SO3Na
ILH
(I10
60
1?IH
|
CH3—CO—I(1JT—N=N
—SO2—NH—CIYIz—CI-Iz—SSOaNa
-—CH:
65
_
.
ILIH
CHPCOP'CIPI‘PN
.
UNITED STATES PATENTS
(lJ0
’
.
References Cited in the ?le of this patent
v
—SOZ—NH—CHZ—OHZ—S—SOBM
70
2,245,971
Felix et a1 _____________ __ June 17, 1941
2,283,326
Felix et a1. __________ __ May 19, 1942
2,706,200
Lecher et a1 ___________ __ Apr_ 12, 1955
FOREIGN PATENTS
490,945
Great Britain __________ __ Aug. 24, 1938
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