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Патент USA US2106876

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2,106,876
Patented Feb. 1, 1938
UNITED STATES PATENT OFFICE
2,106,876
AZO DYESTUFFS
Friedrich Schubert, Leverkusen-I. G. Werk, Ger
many, assignor to General Aniline Works, Inc.,
New York, N. Y., a corporation of Delaware
No Drawing. Application March 30, 1936, Serial
No. 71,797. In Germany April 4, 1935
9 Claims. (Cl. 260-70)
Those of my new compounds of the above for
The present invention relates to new azodye
stuffs, more particularly it relates to dyestuffs mula, in which R stands for a diphenyl radical,
which may be represented by the general formula: are obtainable by combining in either order one
molecular proportion of a naphthol sulfonic acid
capable of coupling twice, with one molecular
proportion of a tetrazotized 4,4’-diaminodiphenyl
compound and one‘molecular proportion of any
diazo compound, whereby the ?rst coupling is
performed in an acid medium, the second in an
alkaline medium, then combining with one molec
In the said general formula X is a member of
the group consisting of hydrogen and N=N—R5,
and R stands for a radical of the benzene series
or of the l,1’-diphenyl series bearing the azo
groups in the 4,4’-positions, such as the benzene
1 01
ular proportion of a 1,3-dihydroxy compound of
the benzene series and coupling the polyazo dye
stuff formed with one molecular proportion of a
monodiazo compound, or either at the same time
or successively with two molecular proportions of 15
nucleus, which may be substituted, for example
by alkyl, halogen, the sulfonic acid group and the
the same or of di?erent monodiazo compounds.
carboXylic acid group, or a diphenyl which may
adapted for dyeing leather, yielding in general
bear substituents, such as alkyl, alkoxy, halogen,
brown to blackish brown shades and they are par
20 the nitro group, the sulfonic acid group and the
carboxylic acid group, R1 stands for the radical
of a naphthol sulfonic acid, capable of coupling
twice, such as for aminonapththol sulfonic acids
or dihydroxynaphthalene sulfonic acids, R2, R4
25 and R5 stand for aromatic radicals which may
bear substituents, such as alkyl, alkoxy, the nitro
group, halogen, the sulfonic acid group and the
carboxylic acid group, and which may contain an
azo group, R3 stands for a radical of a 1,3-dihy
30 droxy compound of the benzene series.
The dyestu?s thus obtained are especially
ticularly distinguished by their good fastness to 20
acids and alkalies, and by their giving full and
subdued shades.
The invention is illustrated by the following
examples without being restricted thereto:
Example 1.—184 kgs. of benzidine are tetrazo
tized in the known manner and combined, in an
acid medium, with 363 kgs. of the sodium salt of
1,8eaminonaphthol-3,6~disulfonic acid. When
the formation of the monoazo dyestu? is com
plete, 209 kgs. of p-sulianilic acid (dihydrate) are
Those of the above identi?ed dyestuffs, in which
diazotized and added, and coupling is effected in
R stands for a radical of the benzene series, are
obtainable by combining in either order one mo
lecular proportion of a naphthol sulfonic acid
r capable of coupling twice, with one molecular pro
portion of a diazo compound of the benzene series
containing a group which is ‘convertible into an
a medium alkaline with sodium carbonate.
After the coupling is complete, a solution of 110
kgs. of resorcinol is added to the dyestuff formed.
After this, to the coupling mixture a diazo solution
amino group, such as for instance a nitro group,
and with one molecular proportion of any diazo
4 O compound, one of these couplings being effected in
an acid, the other coupling in an alkaline medium,
then converting into the amino group the group
above speci?ed, subsequently diazotizing, coupling
in an alkaline medium with one molecular propor
tion of a 1,3-dihydroxybenzene compound and
then with one molecular proportion of a monodi
azo compound or either at the same time or suc
cessively with two molecular proportions of the
50 same or different monodiazo compound.
25
prepared from 138 kgs. of p-nitraniline'is added,
when the reaction of the diazo compound dis
appears after about 10 minutes. After the addi
tion of a further solution of 375 kgs. of sodium 40
carbonate in about 1400 litres of water, ?nally
another diazo solution prepared from 138 kgs. of
p-nitraniline is added. This ?nal coupling is
complete after stirring overnight. The next pp.
5
morning neutralization is effected and the whole
rendered weakly acid to acetic acid, and the dye
stu? is salted out with 10% of sodium chloride,
the percentage being calculated on the coupling
volume, and then the dyestu?‘ is pressed.
50
2
2,106,876
The dyestuff corresponds to the following
formula:
aniline disulfonic acids, naphthionic acid, naph
thylamine disulfonic acids, chloram'line sulfonic
acids, anisidine sulfonic acids, aminoazobenzene
mono- or disulfonic acids and so on.
Example 3.—To the trisazo dyestu?‘ obtained 5
according to the directions of Example 1, formed
a by combining, in an acid medium, 363 kgs. of the
sodium salt of 1,8-aminonaphthol—3,6-disulfonic
acid with 1 mol. of tetrazotized benzidine and, in
an alkaline medium, with the diazo compound
prepared from 209 kgs. of p-sulfanilic acid (di
hydrate), and by coupling» with 110 kgs. of resor
cinol, after this latter, coupling is complete, a
diazo solution prepared from 209 kgs. of p-sulfa
nilic acid (dihydrate) is added. This coupling is 15
quickly complete. Then 375 kgs. of sodium car
bonate dissolved in waterare added to the cou
pling mixture and the ?nal coupling is effected,
after the addition of the diazo compound pre
10
15
H?
20
pared from 138 ,kgs. of p-nitraniline, by stirring 20
over night. The next morning the dyestuff is
worked up according to the method described in
Example 1. It corresponds to the following for
It forms, when dried, a greyish black powder,
25 which dissolves in water with a deep brown color
mula:
'
ation in concentrated sulfuric acid with a grey
ish blue coloration.
‘
Example 2.-In accordance with the indications
of Example 1, 184 kgs. of benzidineare tetraz
30 otized and ?rst, in an acid’ medium, combined
with 363 kgs. of the sodium salt of 1.8-amino
naphthol-3,6-disulfonic acid, and then to the dye
stuff formed a diazo solution prepared from 218
kgs. of 4-nitraniline-2-sulfonic acid is added.
noas/
\SOxH
35 Couplingis effected in a medium alkaline with
sodium carbonate and the formation of the
trisazo dyestu? is completed by addition of 110
kgs. of resorcinol. Exactly as indicated in Ex
ample Looupling is continued ?rst with the diazo
,40 compound prepared from p-nitraniline, and the
?nal coupling is, after the addition of 375 kgs. of
sodium carbonate, performed with the diazo com
pound prepared from 138 kgs. of p-nitraniline.
The dyestu? obtained, corresponding to the
45 following formula:
N=N-Q03
‘
QM
In comparison with the dyestuffs described in
Examples 1 and 2, the dyestuff of this example
NH: OH
80311
yields essentially more olive shades likewise of
good fastness to acids and alkalies.
The fact appears to be of particular interest
that the shade of the dyestuffs‘ obtained in ac
cordance with this process can be changed not
|
60
N:
SOZH
only by applying different ,diazotization'compoe
50311
55
nents, which may be used for the ?nal coupling ' 55
with the trisazo dyestu? formed from 'benzidine,
the sodium salt of 1,8-aminonaphthol-3,6-disul
fonic acid, p-sulfanilic acid and resorcinol. The
?nal components applied in Example 3, i. e. the
p-sulfam'lic acid and the p-nitraniline, may be? 60
substituted by others, as for instance by p-nitran
iline disulfonic acids, and by anilines or aniline
sulfonic groups substituted by chlorine, hydroxyl
or alkoxy groups, by picramic acid,'1,3-diamino
60
N
65
ll-nitrobenzene and so on.
'It seems to be of‘
importance, however, what is the order of apply
ing these two components for ?nal diazotization.
Thus not only the selection of the diazotizing
~ is soluble in water with a clearer brown coloration
than that obtained with the dyestu? of Example ' components but also the order in which they are, "
1, but otherwise it has the same dyeing proper
ties.
Of course, the diazo compounds of the p
nitraniline and the 4-nitraniline-2-sulfonic acid
mentioned in Examples 1 and 2 may be substi
' tuted by other diazotizing components, such as
one after another, allowed to act upon the trisazo
-
dyestuff formed, gives a far-reaching possibility
of varying the properties of the dyestuffs.
Example 4.—184 kgs. of benzidine are tetrazo
tized and combined, in an acid medium, with 285
kgs. of the sodium salt of 2-amino-5-naphthol
3
‘2,106,876
To the coupling mixture formed
7-sulfonic acid. When the formation of the
monoazo-dyestuff is complete 209 kgs. of p
um carbonate.
sulfanilic acid (dihydrate) are diazotized and
added, and coupling is effected in a medium al
218 kgs. of 4-nitraniline-2-sulfonic acid is added,
kaline with sodium carbonate“ After coupling
pling. After a further solution of 3'75 kgs. of or
sodium carbonate in about 1400 litres of Water
is added, ?nally a diazo solution prepared from
is complete a solution of 110 kgs. of resorcinol is
added to the dyestuff formed. When this step
of the formation of the dyestuff is complete, to
the coupling mixture a diazo solution prepared
from 218 kgs. of 4-m'traniline-2-sulfonic acid is
added, which latter disappears after a short dura
tion of coupling. After a further solution of 3'75
kgs. of sodium carbonate in about 1400 litres of
water is added, ?nally a diazo solution prepared
from 138 kgs. of p-nitraniline is added. This
coupling is complete over night. The next morn
in this manner a diazo solution prepared from
which'disappears after a short duration of cou
138 kgs. of p-nitraniline is added. This coupling
The next morning the
dyestuff is salted out with 5% of sodium chloride,
is complete over night.
while neutralizing at the same time until the re
action is only weakly alkaline, and then squeezed
and dried. It corresponds to the following for
mula:
'
ing the dyestuff is salted out with 5% of sodium
chloride while neutralizing at the same time until
the reaction is only weakly alkaline, and then
squeezed.
.
The dried dyestuff, corresponding to the fol
lowing formula:
NH:
N=N
OH
30
Hols N=NOSOsH
S 03H
35
N=N
I1I=N
N02
N= -QOH
'
r
. H N=NAO—NO:
OH
a lag“.
Example 6.—138 kgs. of ‘p-nitraniline are di
azotized in the known manner and combined, in
dissolves in water with a deep brown, in concen
trated sulfuric acid with a blackish blue colora
tion.
'
It is obvious that far-reaching variations can
be made in the shade of the dyestuffs manufac
tured in accordance With this process, by substi
tuting the diazo compounds coupled to the
fundamental structure of .the dyestuff benzidine
azo-2-arnino-5-naphthol-7-sulfonic
acid - azo
resorcinol by suitable monodiazo or diazoazo
compounds other than indicated in the example,
as for instance by p-aminobenzoic acid, l-hy
droxy-4-aminobenzene-Z-carboxylic acid, aniline
sulfonic acids containing chlorine or hydroxyl or
alkoxy groups, picramic acid, 1,3-diamino-4-ni
trobenzene or aminoazobenzene-mono- or disul—
ionic acids. In this example also not only the
selection of the diazotization components but the
succession of their coupling presents a far-reach
ing possibility of varying the dyestuff properties.
(55
Example 5.—285 kgs. of the sodium salt of 2
amino-S-naphthol-‘l-sulfonic acid are combined,
in an acid medium, with the diazo compound
prepared from 209 kgs. of p-sulfanilic acid (di
hydrate). When the formation of the monoazo
70 dyestuff is complete a tetrazo solution prepared
from 184 kgs. of benzidine is added and the re
action mixture is rendered alkaline with sodium
carbonate. When the coupling, is complete a so
lution of 110 kgs. of resorcinol is added and cou
75 pling is effected in a medium alkaline with sodi~
an acid medium, with 285 kgs. of the sodium salt
of 2-amino-5-naphthol-7-sulfonio acid. When
the formation of the monoazo dyestu? is com
plete, there is added the diazo compound pre
pared from 209 kgs. of p-sulfanilic acid (dihy
drate), and coupling is effected in a medium al
kaline with sodium carbonate. After coupling is
complete, a solution of about 420 kgs. of sodium
sul?de is added‘to the coupling mixture, and the
whole is stirred until the reduction of the nitro
group is complete. Thereupon, for removing the
sulfur, the dyestuff solution is rendered acid to
Congo red, and the dyestuff which has been pre
cipitated and squeezed oil’ is dissolved in an
aqueous solution of sodium carbonate and the
solution ?ltered. To this solution a solution of 00
about '70 kgs. of sodium nitrite is then added,
the solution thus obtained is rendered acid to
Congo red with hydrochloric acid, at a low tem
perature, and stirred until diazotization is com
plete. Thereupon a solution of 110 kgs. of resor
cinol is poured into the diazotization mixture,
and coupling‘ is effectedin a medium alkaline
with sodium carbonate. When coupling is com
plete, there is poured into the coupling mixture
a diazo solution prepared from 218 kgs. of 4 70
nitraniline-Z-sulfonic acid, which disappears
after a short duration of coupling. After the
addition of a solution of about 350 kgs. of sodium
carbonate in 1400 litres of water, ?nally the di
azo solution prepared from 138 kgs. of p-nitrani
4
2,106,876
line is added. Coupling is effected over, night.
The next day the dyestu? is salted out with
about 10% of sodium chloride, while at the same
time adding sodium carbonate until the reaction
The dyestu? corresponds to the following for
mula:
,
HzN
V
'
on
'
is weakly alkaline, and then it is pressed, 7
The dried dyestuff corresponding to the fol
lowing formula:
III==N
'
N=NGS 03H
s 0.11
11018
10
NH:
N=N
|
N01
l?r
N=N
|
N-
OH
'
S 0:11
OH
15
nozls N=NOSO1H
N
In the following table there are given further
combinations prepared in accordance with the
invention. All the dyestuffs mentioned therein
are suitable for dyeing leather yielding brown to
blackish brown shades. In the formulae of the
,
It
20
HO
table B means benzidine, Res. means resorcinol
and the arrow (<-) means “diazotized and cou
2
25
0
2:
pled to”.
(_._.____—
alkaline coupling
(1)
H-acid
coupling
30
'
4
H " anilin
7‘
30
acid
N03
B
\
35
\\
dissolves in water with a dark brown and in con
centrated sulfuric acid with a black coloration
and, on leather, it yields productive, full and
subdued shades.
40
as
Res.<-—
'
p-sulfauilic acid
,
Example 7.—138 kgs. of p-nitraniline are di
azotized in the known manner and coupled, in
an acid medium, with 363 kgs. of the sodium salt
of l,8-aminonaphtho1-3,6-disulfonic acid. When
the coupling of this monoazo dyestu? is com
plete, 209 kgs. of p-sulfanilic acid are diazotized
' i.
_
407
7'
couphng
acid /
/
V
B
\
45 and the product added, and coupling is effected
in a medium alkaline with sodium carbonate.
After this coupling is complete, a solution of
about 420 kgs. of sodium sul?de is added to the
dyestuff, and the Whole is stirred until the re
50
duction is complete. This reduction mixture is
rendered acid to Congo red with hydrochloric
acid, and the dyestu? thereby separated is
squeezed o? and, for removing the sulfur, dis
alkaline coupling
(2)
45
\\4
p-sulfanilic acid
1
Res.
7
'\
..
7.
p-sulfamhc acid
50
alkaline coupling
(3)
H-acid (_—__—aniline
55 solved in a hot aqueous solution of sodium car
bonate and ?ltered. After cooling, there is add
ed to the ?ltrate a solution of '70 kgs. of sodium
nitrite, the mixture is rendered acid to Congo
red at a low temperature, and stirred until di
60 azotization is complete. 'I'hereupon a solution
of 110 kgs. of resorcinol is poured into the diazo
tization mixture, and coupling is effected in a
medium alkaline with sodium carbonate. When
coupling'is complete, to the coupling mixture a
65 diazo solution prepared from 218 kgs. of 4-nitran
iline-2-sulfonic acid is added, which latter com
ponent disappears after a short time. After a
solution of about 350 kgs. of sodium carbonate
in 1400 litres of Water has been added, there is
70 ?nally added a diazo solution prepared from 138
kgs. of p-nitraniline. Coupling is complete over
night. The next day the dyestuff is salted out
with about 10% of sodium chloride while at the
same time adding sodium carbonate until there
75 is a weakly alkaline reaction, and then squeezed.
B\\
‘a
Res.
\../
p-sulfanilic acid
60
p-nitraniline
alkaline coupling
H-acid<——-——p-nitraniline
(4)
65
7'
coupling/
7 acid
B
70
p-sulfanilic acid
Res.
l/
p-nitraniline .
75
5
2,106,876
vi
.
(5)
alkaline coupling
(11)
_ _
alkaline coupling
kH-acid<—~———p-suliaml1c acid
coup§/
coupling
ilH-acid(-—————-~—H2N
N01
acid
acid
B
B\\
\:
m-nitranlh'ne
p<sulianilic acid
N
Res.
10
Res.
l/
'\
. .
10
.
p-sulfamhc acid
m-nitraniline
(12)
alkaline coupling
H-acid<———--—— aniline
alkaline coupling
(6)
coupling
H-acid<—-————-——p-m'traniline
15
_
7'
coupling
acid
acid /
/
B\\
B
SOaH
Res.<-H:N
p-sulfanilic acid
Res.
NO:
1
R
(13)
p-sulfanilic acid
alkaline coupling
H-acid<——————-——aniline
coupling 7|
/
alkaline coupling
(7)
H-acid <—————- p-nitraniline
B\
/H1N
\\| 11/ 803E
coupling/
30,
acid
IB\\
R
\
Res.
|Z
p-nitranline
(14)
acid
)H-acide-—————————H:N
B
NO:
/
\l
4_-sulfonic acid
Cr! Cal
coup?
‘
50
B\
'
p‘i?gmmc
N
7‘
(16)
\\|
p-nitraniline-o-sulionic acid
coupling
7lIEI-acid<———--————~aniline
acid
B
Res.
p-nitraniiine
/
60
\
\:
(10)
coupling
ilH-acid<———————-——HzN-C>~NO2
NH:
/
l
H-acid<-———————-—aniline
7‘
coupling
70
acid
\ I
/
p-nitraniline
\
I! 1'
3/
Res.
'\
75.
65
alkaline coupling
( 7)
/
B\
-y-acid
I!
Res.Rp-nitraniline
alkaline coupling
acid
55
alkaline coupling
B/
70
ResA-y-acid
acid
61)
45
acid
.
alk. coupling
l-ammo-8-hydroxy'
'Rp-nitraniline
coupling
p-nitmniline
.
1!
alkaline coupling
H-acid<—————-—
(15)
Res.
(9)
40
S 0211
es.
p-sulfanilic acid
35
/
\\
NH:
B\\\
NO:
7|H-acid+——-——aniiine
coupling/
alkaline coupling
acid /
HaN
alkaline coupling
(8)
coupling
NO:
Res.
p-m'traniline
40
25.
SQzH '
acid /
.
.
p-mtranllne
Res‘
o-chloro-aniline
plsulfonic acid
15
6
2,106,876
‘
(18)
alkaline coupling
,
(24)
V 7|H-acid<——-—aniline
coup?
B\\
alkaline coupling
7
‘
.
,
H-acid<-—-—————-—aminoazobenzené
_
)1
monosulfonic acid
coupling
acid
'
l
‘
acid
/
‘a
B\\
p-nitraniline
p-nitran'iline
Res.
Ro-chloro-aniline
p-sulfonic acid
Res.r\p-nitraniline
alkaline coupling
alkaline coupling .
15
(19)
(25)
/_‘H-acid(———-———aniline
coupling
10
’
7'
I
H-acid('————-———aminoazobcnzcne
disulfonic acid
coupling
'
acid
acid
/
B\\
\I
B\\
'2, 5-dichloroaniline-si?fonic acid
\i
i!
Res.
'20
p-nitraniline
i!
Res.
R
.
. .'
p-mtranlline
alkaline coupling
H-acid<———————aniline
25 (20)
coupling/
alkaline coupling
(26)
,
' H-acid<———p-sulfanilic acid
acid
coupling
/
B
‘
V
acid
\\
7
30
B\\
2, S-dichloroaniline
\/ sulfonic acid
Res.
'\
p-nitraniline
\
Res.
L/
p-nitraniline
'\
(21)
coupling
40
(27)
acid
V
V
s 03H
3
l
\
/HIN
‘
'\\
alkaline coupling ’
scan
\
MGM.
1!
alkaline coupling
H-acid(————-———anili.nc
(22)
Res.
m-nittaniline
50
(28)
»-
- alkaline coupling
H-acid<——-————p-sulfanilic acid
coupling/
coupling
acid /
60
\i
/HzN
Res.
'\
? 03H
enzi inc
N O:
i!
55
bm-niggo- \
S 0311
\
I
ac?
.
B\
\4
l
NH:
.
alkaline coupling
(23)
'\
(29)
V
coupliy
B\\
p-nitraniline
alkaline coupling
H-acid<——-—~—p-sulfanilic acid
65
coupling
acid
acid /
a
.2’
Resk
is
\ V
H-acid<—————'—-—m-sulfanilic acid
7‘
60
Res
. .
p-mtranillne
65
45
p-nitraniline
NH:
50
40
‘
B\\
,
I
)H-acid<—'———-—_p-sulfanilic acid
acid /
Nm
Res.
.
coup?
NO:
\\ ‘1/
45
.. .
p-sulfanilic acid
alkaline coupling
H-acid(-———aniline
‘
-nitran1line
'
a
p-nitranlline
benzidine-m-
S 03H
disulfonicacid\
I
\1
Res
p-nltranillne
70
2,106,876
(30)
alkaline coupling
‘
(36)
alkaline coupling
.T-acide————-1-naphthy1amine
J-acid(-———-——-—~—p-sulianilic acid
4-sulionic acid
coupling
coupling
acid
acld
m-nitro-
'
S 03H
,
NH;
,
benzidine
/H:N
SIOaH
' NOa'
1!
\(
NHH Res.
Res.
10
' '\
(31).
.
. .
p-mlzranilincv
(37)
alkaline coupling
alkaline coupling
J-acide——-—-————1-naphthylamine
T
coupling
coupling
benzidlne-m-
15'
NH,
SOBH
disulionicacld\
l
\
'
20
'
'
‘
SOaH
H?N ‘
H’NONO’
N02
/
\l
i!
Res.
NHH Res’.
p-nitraniline
'\
p-nltraniline
(s2)
alkaline coupling
J-acid<--—-———
25
alkaline coupling
(38)
H-acid<—-———-—p-su1fanilic acid
aniline
25
coupling
coupling/
acid
acid
NH2
1
NH,
30
80311
? 01H
$ 0 3H
NHZ
MGM),
z '
. '
Res. R
p-m'traniline
p-nitraniline
(33)
30
ENONW
\
H2—-—)Res.
alkaline coupling
(39)
alkaline coupling -
J-acid(—-——-—-—naphthi0n.ic acid
coupling/
40
3, 6-disulf0nic acid
acid /
acid
35
10'
p-nitraniline
-J-acid<—-—--+——p-sulfanillc acid
15
‘
'
‘
coup?
?H-acid<—-————-———-p-sulfanilic acid
acid /
N'Hz
acid
40' "
NH:
S 03H
SOzH
NHa\
45
HgN
HaN
\I
N01
N02
ll/ 7
: R85.
\
NEH Res.
p-nitranilinc
(34)
coupling/
J-acid<————-——1-naphthylamine~
7|
J -acid(—-—————-p-sulfauilic acid
_
alkaline coupling
coupling
phenyl-alkaline coupling
(40)
50
3, G-disulfonic acid
.
m-mtraniline
7'
50"
acid
NHz'
acid
55
S 0 3H
NH: ‘
SOaH
/H¢N
HaN
60
NO:
NH=—-—-—>Res.
60
p-nitraniline
phenyl-alkaline coupling
NHH Res.
p-nitraniline
NO,
|!
(41)
.T-acid<—-—-———p-sulfanilic acid
7|
(35)
_
alkaline coupling
J-acid(———-——-—p-sulfanilic acid
65
.
couply
acid /
NHa
coupling
acid
N-Ha
? 03H
SI 0 3H
70
-NH2—>\
NHz-e Res.
/HENONOI
v
7
p-nitraniline
75
I!
Ros.IR
p-nitraniline
,
v
75
8'
(42)
2,106,876‘
fif-ilihrgrqflrnavh- 81k81.
1.- .
gene’ -S OIAICidJg-HP lngp-sulfam'?c acid
1m /7'
a
‘
wherein X is a member of the group consisting‘
of hydrogen and N=N—R5, and R1 stands for a
'
radical of an aminonaphthol sulfonic acid capa
coup g
5.
ble of coupling twice, R2, R4 and R5 stand for
acid
NH,/
aromatic
brown
to radicals
blackishyielding
brown shades
on leather
of good
in general
fast
1
.
ness properties.
SOaH
-
'4. Azodyestuffs of the general formula:
I
10
.
HzN-ONO:
'
/ '
,
.
t
'
10;
N=N—R1—N=N—R1
NHz_>Res.\
V
15
p-nitrsniline
‘
I claim:
15
1. Azodyestuffs of the general formula:
'
N=N——R1—N=N—Rz
V
N=N_R’\
l
' N=N'~R4
,
'
I1I=N
N=N"‘R4
OH
x
V
'
H
V 25 wherein X is a member of the group consisting
V
of hydrogen and N=N-—-R5, and R stands for a
radical selected from the group consisting of the
benzene series and the 1,1'-diphenyl series, bear
ing the azo groups in the 4,4’-positions, R1 stands
solfor a radical of a naphtholsulfonic acid capable
wmof?couplingwtwice, RaeRnand R5. stand ior iaro
matic radicals,rRg stands for a radical of a 1,3
.dihydroxy compound of the benzene series, yield
ing on leather in general brown to blackish brown
x
' '
25;
wherein X is a member of the group consisting
of hydrogen and N=N~R5, and R1 stands fora
V
radical of Z-amino-5-naphthol-'7-sulfonic acid,
R2, R4 and R5 stand for aromatic radicals yield- 30;
ing on leather in’ general brown togblackish
brown shades of good fastness properties.
5. The dyestu? having in the free state the
following formula:
W
n
A.
35 shades of good fastness. properties.
1 7
2. Azodyestu?'s of the general formula:
'
' '
5
35; '
NH‘
A
2
,
'
~
'
|
N=N—R1-—N=N--Rz r
~N=N
4o;
'
OH
‘
_
40,
Hogs N=N-O-s0m '
45
'
‘
'
.
-
50
45,
sonar ‘
'
50'v
wherein X is a member of the group consisting of
hydrogen and N=N-—R5, and R1 stands for a
radical of a naphtholsulfom'c acid capable of
coupling twice, R2, R4 and R5 stand for aromatic
~e1 -n
1
h
-
'
yl sfilAzgogélesfgésegfbgggkgglggwgr?ggis'
radicals yielding on'leather in general brown to
'
' '
blackish brown shades of good fastness properties.
60
3. Arzodyestuifs of the general formula:
N=N_R1—-N=N—Rz
60
N=N-R1-N=N-R,
V
IIT=N-—'R4
65
70
N_N_R
'
|_
N: ._
OH
'
V
r
7
H
.
‘
H X
75
MNQOH
V
x
V
65,
wherein X is a member of the group consisting 70'
,
of hydrogen and N=N—R5, and R1 stands for a
‘
radical of a naphtholsulfonic acid coupling
twice, R2, R4 and R5 stand for aromatic radicals,
yielding on leather in general brown to blackish
brown shades.
m
9
2,106,876
'7. Azodyestuffs of the general formula:
N=N—R1—N=N—R2
R2, R4 and R5 stand for aromatic radicals, yield~
ing on leather in general brown to blackish
brown shades.
9. The dyestuff having in the free state the
following formula:
17112
‘
N=N—
10
OH
wherein X is a member of the group consisting
of hydrogen and N=N—R5, and R1 stands for a
1?1~
radical of an aminonaphthol sulfonic acid cou
blackish brown shades.
8. Azodyestuffs of the general formula:
Hogs
I
N=N—-
s 0311
N
pling twice, R2, R4 and R5 stand for aromatic
15 radicals, yielding on leather in general brown to
H 0-
s 0811
I
N
1
OH
20
25
7
(IJHIII
I
20
lilo:
25
yielding on leather blackish brown shades of
wherein X is a member of the group consisting
of hydrogen and N=N~—R5, and R1 stands for a
radical of a Z-amino-5-naphthol-7-sulfonic acid,
good fastness properties.
FRIEDRICH SCI-IUBERT.
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