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Патент USA US2128508

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2,128,508
Patented Aug. 30, 1938
UNITED STATES PATENT OFFICE
2,128,508
AZO D-YESTUFFS
Richard Stusser, Cologne, and Friedrich Muth,
Leverkusen, Germany, assignors to General
Aniline Works, Inc., New York, N. Y., a cor
poration of Delaware
No Drawing. Application June 21, 1935, Serial
No. 27,811. In Germany June 27, 1934
5 Claims.
(Cl. 260—152)
The present invention relates to azo dyestuffs
forming heavy metal ‘complex compounds; more
particularly it relates to dyestuffs which may be
represented by the probable general formula:
5
fastness to fulling, carbonization and light. Those
of our dyestuffs which are insoluble in water dis
solve in organic solvents, such as pyridine and
can be used for shading lacquers.
The invention is illustrated by the following
01
examples, without, however, being limited there
to:—
Example 1
wherein R stands for the radical of a diazo com
0 pound, capable of forming heavy metal complex
One molecular proportion of 6-nitro-2-amino
phenol-‘l-sulfonic acid is diazotized and coupled
compounds, which may bear an azo group, such
as a radical of a diazotized aromatic amine bear
in aqueous caustic alkaline solution in the pres
ence of sodium carbonate with one molecular pro
ing in ortho-position to the diazotized amino
portion of 3-hydroxy-diphenylene sul?de in the
group a metal complex forming group, such as
v15 the hydroxy group, an alkoxy group and the car
cold and in the presence of pyridine. After sev
eral hours the coupling mixture is acidi?ed, some
common salt is added, and the dyestuff sepa
rated is ?ltered and dried. It is obtained in the
form of a dark powder, soluble in aqueous sodi
boxylic-acid group
'20 and
Rx
n
um carbonate solution, dyeing wool from an acid I
bath; it corresponds in its free state to the fol- ‘ '
lowing formula:—
OH
stand for radicals of the benzene series, wherein
OH and N=N.R stand in ortho position to each
25 other attached to one of the benzene radicals R’
and R”, it stands for one or two, :1: stands for
,
S, 0, CH2 or CH=CH, and wherein the benzene
S 03H
ents, such as alkyl, alkoxy, halogen, the sulfonic
for example by alkyl or aryl.
Our new dyestuffs are obtainable by diazotizing
or tetrazotizing respectively an aromatic amine,
capable of forming heavy metal complex com
pounds and coupling ‘with one or two equimolec
ular proportions respectively of a coupling com
ponent of the general formulav:—
\
I
radicals R’ and R" may bear further substitu
acid group, the carboxylic acid group, the sulfone
amide group and the carboxylic acid amide group,
the hydrogen atoms of which may be substituted
OH
S
/
<
>
By after-treating the dyeings with bichromate
there are obtained Corinth shades fast to fulling,
carbonization and light.
Example 2
One molecular proportion of diazotized 5
sulfo-2-aminobenzoic acid is coupled with one
molecular proportion of 3-hydroxy-diphenylene
oxide in an alkaline medium.
When the cou
pling is complete, the dyestuff is salted out with
common salt, ?ltered and dried. It is obtained
in the form of a dark powder, soluble in water
and dyeing Wool from an acid bath reddish
wherein a: and n mean the same as stated above.
The dyestuifs thus obtained can be transformed
in substance or on the ?ber into their heavy metal
brown shades; it corresponds in its free state to
45
the following formula:—
OH
complex compounds by treating with suitable met
als or metal compounds, such as copper. copper
hydroxide, copper salts, chromium hydroxide,
chromium salts‘ and the like. Those of our dye
stuffs having water-solubilizing groups‘ are suit
able for dyeing the ?ber, yielding generally brown
to violetish-brown to blackish-brown shades,
which when transformed into their heavy metal
:55 complex compounds are distinguished by good
50
HOaS
By after-chroming there is obtained an olive
brown fast to fulling, carbonization and light.
2
2,128,508
dyes W001 when after-chromed negro-brown
shades of good fastness properties.
Example 6
By substituting the 5-sulfo-2-aminobenzoic
acid by one molecular proportion of 1~amino-2
hydroxy - 6 - nitronaphthalene - 4: - sulfonic
acid
there is obtained a dyestuff dyeing wool when
after-chromed blackish-brown shades of good
20 grams of the dyestuff described in the ?rst
paragraph of Example 2 are re?uxed for 10
fastness properties.
hours in 300 cos. of water with 6 grams of a chro
Example 3
10
mium chloride solution containing 270 grams of
CrzOz per litre. The complex chromium com
pound formed is ?ltered and dried. It is a dark 10
powder soluble in water, dyeing wool from an
acid bath olive brown shades of good fastness
to fulling, carbonization and light.
One molecular proportion of diazotized 4
nitro-Z-aminophenol-G-sulfonio acid is coupled
in an alkaline medium with one molecular pro
15
portion of the 3-hydroxy-diphenylene oxide 2
carboxylic acid. The dyestuif having in its free
state the following formula:-—
HOaS
OH
OH
I
l
'
Example 7
15
One molecular proportion of 6-nitro-2-amin0
phenol-ll-sulfonic acid is diazotized in the usual
00011
/
manner and coupled in an alkaline medium with
one molecular proportion of 3-hydroxyphenan
threne. When the coupling is complete the re 20
/
action mass is acidified with acetic acid and the
llloz
>
dyestuff separated is ?ltered and dried. It is
obtained in the form of a- dark powder, dyeing
dyes wool when after-chromed reddish-brown wool from an acid bath; on after-chroming the
dyeing there is obtained a grey or in the case 25
25 shades.
In an analogous manner diazotized l-amino-ll
of dark shades a black of good 'fastness to full
nitrobenzene G-carboxylic acid yields when cou- , ing, carbonization and light.
pled with 3-hydroxy-diphenylene oxide monosul
The dyestuff corresponds in its free state to the
fonic acid (obtained by monosulfonating 3
following formula:—
30 hydroxy-diphenylene oxide; probably the 2
.30
O
sulfonic acid) a dyestu? dyeing wool yellowish
brown shades, which on after-chroming are
turned to dark brown.
Example 4
35
35
One molecular proportion of tetrazotized 4,4’
diaminodiphenyl-3,3'-dicarboxylic acid is coupled
in a bicarbonate alkaline medium containing a
small quantity of pyridine with one molecular
40 proportion of 3-hydroxy—diphenylene oxide and
after this in a soda alkaline medium with one
One molecular proportion ‘of 6-nitro-2-amino
phenol-‘l-sulfonic acid is diazotized in the usual
manner and coupled in pyridine in the presence
of an alkali with one molecular proportion of 2
molecular proportion of 1(4’-sulfophenyl) 3
methyl-5-pyrazolone. The dyestuff correspond
ing in its free state to the following formula:
45
40
45
|
N: C
00011
’
I
l
I
50
50
/
3
55
dyes cotton brown shades which when after
treated with a copper compound are turned to
yellowish brown of good fastness to washing and
light.
Example 5
60
hydroxy ?uorene. After stirring for some hours 55
the coupling mixture is rendered acid to'Congo
red, some common salt ‘is added and the dyestu?
separated is ?ltered. After re-dissolving and
drying, the vdyestuff having in its free state the
following formula:
(it)
One molecular proportion of diazotized 6-mi
tro-2-aminophenol-ll-sulfonic acid is coupled in
a soda alkaline medium containing pyridine with
one molecular proportion of 6-bromo-3-hydroxy
diphenylene oxide. The dyestuff corresponding in
its free state to the following formula:—
I
SOaH
is obtained in form of a dark powder, dyeing wool
reddish-brown shades, which on after-chroming 70
are turned to olive-brown of good fastness to
70
fulling, carbonizing and light.
S 03H
Example 9
Two molecular proportions of diazotizedé-ni
75
3
2,128,508
tro-2-aminophenol-6-sulfonic acid are coupled in
a caustic alkaline medium containing pyridine
with one molecular proportion of 3,6-dihydroxy
diphenylene oxide. The dyestuff having in its
free state the following formula:—
NO:
<:>~N=N
I
10
l
1103s
mula:
EOE
_\_Y
—<N=N—R
l|\TOz
N=N®
\
l
OH
HO_
2. Water-soluble azo dyestuffs forming heavy
metal complex compounds of the general for
5
wherein X stands for the radical of a diphenylene
oxide compound, R stands for the radical of a
diazo compound, capable of forming heavy metal 10
complex compounds, OH and N=N—R stand in
ortho position to each other and Y stands for a
water-solubilizing group selected from the class
HO soan
OH
0/
15 dyes W001 when after_chromed blackisbbrown
Shades_
Example 10
One molecular proportion of diazotized 4-ni20 tro-2-aminophenol-6-sulfonic acid is coupled in
consisting of the sulfonic acid and the carboxylic
acid groups yielding generally brown to Violetish- 15
brown to blackish-brown shades, which, when
transformed into their heavy metal complex com
pounds, are distinguished by good fastness to
fulling, carbonization and light.
20
3. The water-soluble azo dyestu? having in its
an alkaline medium with one molecular propor- I free state the following formula:
tion of the 3-hydroxy-diphenylene oxide. The
dyestu? having in its free state the following forOH
OH
|
|
Hoas—
000E
l
OH
|
\0
N: Q
1103s
/
g /
30
:
NO
30
dyeing wool from an acid bath reddish-brown
shades, which by after-chroming are turned to
2
.
-
live brown fast to fulling carbonization and
light.
_
_ _
dyes wool from an acid bath brown shades which
0
by after-chroming are turned to blackish brown
f 4' Tthg vzgte?i?lw.ole afzo dyesiiu? havmg m Its 35
35 of good fastness to fulling, carbonization and
light.
We claim:
1. Water-soluble azo dyestu?’s forming heavy
ree S a‘ e
e o owmg Ormula"
0H
OH
11033--
N=N*
metal complex compounds of the general formula:
40
40
'
_/OH
XI
1
__Y
0
:3/
N02
—\—N=N—R " J
'
dyeing wool from an acid bath reddish-brown 45
45 wherein X stands for the radical of a diphenylene
oxide compound, R. stands for the radical of a
shades, which by after-chroming are turned to
blackish brown fast to fulling carbonization and
diazo compound, capable of forming heavy metal
light.
complex compounds, OH and N=N—R stand in
ortho position to each other, n stands for one of
5. The water soluble azo dyestuff having in its
free state the following formula:
50
I
.
50
‘RH’
/N:0
SOaHON\
l
'
00011
|
000
| H
(|)H
55
'
o
'
60 the numbers one and two and Y stands for a
Water-solubilizing group selected from the class
consisting of the sulfonic acid and the carboxylic
acid groups, yielding generally brown to violetish
brown‘to blackish-brown shades, which when
65 transformed into their heavy metal complex com
pounds are distinguished by good fastness to
fulling, carbonization and light.
/
Q 60
dyeing cotton brown shades which by after
treatment with a compound yielding copper are
turned to yellowish brown shades of good fastness
to light and washing.
RICHARD STUSSER.
FRIEDRICH MUTH.
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