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Патент USA US2095484

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Patented Oct. 12, 1937
*4 2,095,484
UNITED'T'STATES * PATENT OFFICE
'
1 2,095,484
AZODYESTIIFE‘S
.
,
Carl Taube, Leverkusen-ILG. Werk, andJohann
Heinrich Helberger, Cologne-Mulheim, ‘Ger
many, assignors to General Aniline'Works, Inc., ‘
7 New York, N. Y., a corporation of Delaware ‘
. No Drawing. Application October 15,1935, Serial -
a No. 45,162. In Germany October 17, 1934
_
3 Claims.
The present'vinvention relates to ‘new heavy
metal complex compounds of azodyestuffs, more
particularly it relates to heavy metal complex
compounds of azodyestuffs which are derived from
5‘ heterocyclic amines as diazotization components,
containing in the heterocyclic nucleus the group
ing
~
'
(Cl. 260-42)
property it is possible to prepare, for example
with the aid of diazotized aminotetrazole and a
coupling component without solubilizing groups,
soluble azodyestuffs which can be applied to ?bres
and by aftertreating on the fibre with suitable ‘5 '
metal compoundstransformed into insoluble azc
dyestuffs by conversion into the heavy metal com
'
plex
10
compounds.
‘
-
'
The new azodyestu?s containing heavy metal
in general exhibit valuable fastness properties 0
NH: 7
Our new dyestu?s are obtainable‘ by starting and can be used for producing novel e?ects.
with such azodyestu?sas are derived from hetero
Among the great number of heavy metal com]
cyclic amines a‘s’diazotization components con
15'
plex compounds of azodyestuffs there are of
taining in the heterocyclic nucleus the grouping . especial technical value the copper complex com
pounds of the azodyestu?s of the general form- 15
ula:
and transforming the same according to meth
ods known per se in‘substanoe or on a substratum,
20 especially on the_?ber,.into their heavy metal
complex compounds, for example by treating
with the heavy metal in a ?nely divided form‘
or with a suitable heavy metal compound.
As amines containing the grouping
,
R'—N=N——R—X—R——N=N-R"
In this formula. X represents a carbon-carbon
linkage or a bridge especially such one as contains 20
a hetero atom, for example oxygen, sulfur, the
group NH and the group NI-I-CO--NH, R. stands
for a radical of the benzene series, bearing the am
group in p-position to X, R’ stands for the radical
v_ .of an azodyestu? component with two coupling 25
7 positions, bearing attached to the other coupling
"*position the radical of a diazotized heterocyclic
there may be‘ mentioned byway of example amine containing in the heterocyclic nucleus the
, aminotetrazole (compare German Patent No.
30 426,343) , ' aminotriazole (compare Annalen der
Chemie, vol. 303, (1898), pages 33-56), guanazole
(compare Journal fur praktische Chemie, vol. 88,
(1913), page 310) and phenylguanazole (compare
Gazetta Chimica Italiana, vol. 21, II, (1891), page
35 146, and vol. 31, I, (1901), page 482).v _
It is surprising that, the coupling products of
grouping
__N-_-";|3'_.NH_
NH:
30
and R” ‘stands for R’ or for another azodyestu?
coupling component.
,
.,
,
,
V
The invention is illustrated by the following
examples; but is not restricted thereto:
Example 1.
35
these diazotized amines with coupling ‘components,
10.3 parts by weight of aminotetrazole mono
such as phenols,- aromatic amines, aminonaph
tholsulfonic acids,‘ pyrazolones, aeeto-acetic acid hydrate are dissolved in 400 parts by weight of
40‘ arylamides, hydroxyquinolines ‘and the like, are water and 100 parts by weight of. 3-N-hydrc- 40
capable of forming valuable heavy metal complex‘
compounds with heavy metal compounds, such as
those of copper, inickel, iron, chromium, cobalt
and the like.»
45
'
r
' ‘
Inthe azodyestuffs used as starting compounds
the hydrogen atom of the imino group in the
vicinal position to the amino group or azo-bridge
respectively exerts so strong acidic properties as
_ to have the solubilizing effect of a carboxylic acid
50‘ group or a sulfonic acid group. Due to this acid
chloric acid and are diazotized with 6.9 parts by
weight of sodium nitrite, with cooling. The clear
and colorless diazo solution is coupled in an acid
medium with 1- (2'-chlorophenyl) -3-methyl-5
pyrazolone, and the dyestu?‘ obtained is isolated in 45
the usual manner and dried.,It.dyes wool from
an acid bath clear yellow shades of excellent fast
ness to light, the, fastness propertiesbeing im
proved by an“ after-treatment with chromium
salts; '
"
5°
2.
2,095,484
The heavy metal complex compound corre
sponds to the following formula:
Example 3
17.5 parts by weight of phenylguanazole are
diazotized as described in Example 2 and cou
pled in strong hydrochloric acid solution with the
calculated quantity of 2-amino-8-naphthol-6
sulfonic acid, with cooling and stirring. The
dyestuff isolated in the usual manner dyes wool
from an acid bath clear yellowish-red shades
which by after-treatment with chromium salts
(Fl
10
turn to a deep reddish-brown.
1O
The heavy metal complex compound corre
sponds to the following formula:
NH:
Oh“?
15
HN=C
15
G—N=N
\ /
NH
Similar dyestuffs are obtained by substituting
HO
the 1- (2'-chlorophenyl) -3y-methyl-5-pyrazolone
\SOaH
by the unsubstituted phenylmethylpyrazolone or
by 1-(2', 5'-dichlorophenyl) -3-methyl-5-pyrazo
TOY
lone or 1-(2’~sulfophenyl)-3-methyl-5-pyrazo
lone, or 1-(2'-su1fo-5'-chloro)-3-methyl-5-py
razolone.
'
Example 2
17.5 parts by weight of phenylguanazole are dis
solved in 100 parts by weight of sulfuric acid of
60° Bé.'and diazotized with 6.9 parts by weight of
sodium nitrite, while cooling and stirring. The
30 clear, yellowish colored diazo solution is dropped
25
into an aqueous solution of the calculated quan
tity of the 3-methyl-5-pyrazolone of 2-chloran
iline-5-sulfonic acid, while cooling and stirring.
.1
Example 4
17.5 parts by weight of phenylguanazole are
diazotized as described in Example 2 and cou
25
pled in a strong hydrochloric acid solution with
the calculated quantity of 2-amino-5-naphth01
'l-sulfonic acid, with cooling and stirring. The
dyestufl is isolated and coupled in solution alka
line with sodium carbonate in the presence of
pyridine with the calculated quantity of tetrazo
tized benzidine o-o'-dicarboxylic acid. The dye
stuff isolated in the usual manner dyes cotton
The dyestuff is isolated in the usual manner and
dried. It dyes wool from an acid bath clear yel
from a Glauber’s salt bath violet shades which on
after-treating with copper salts are turned to a
low shades of excellent fastness to light, the fast~
ness properties being improved by an after-treat
ment with chromium salts.
navy blue fast to washing.
The heavy metal complex compound corre
sponds to the following formula:
40
40
45
45
50
50
55
The heavy metal complex compound corre
sponds to the following formula:
60.
10.3 parts by weight of aminotetrazolemonohy
drate are diazotized as described in Example 1
and coupled in weakly alkaline solution with 2,3
hydroxynaphthoic
acid-p-naphthylamide. The
isolated monoazodyestuff dyes cotton from a
Glauber’s salt bath orange shades which by
after-treating with nickel salts are turned to red
and become fast to washing and light.
65
The heavy metal complex compound corre
sponds to the following formula:
70
_ By substituting the 1-(2'-chloro-5’-sulfophen
yl)-3-methyl-5-pyrazolone by other l-(sulfo
phenyl)-3-methyl-5-pyrazolones there are ob
75
tained'dyestuffs exhibiting similar properties.
N———N
75
a095,!“
3
.
L’iample 8 V ‘
10.3 parts by Weight of aminotetrazolemono
9 parts by weight of 2-amino-5-naphthol-7
hydrate are diazotized as described in. Example '1
and coupled with 14.4 parts byweight'of o-naph
thol. The dyestu?lisolated in theusual manner
dyes wool reddish-yellow shades which onafter
treatment withl‘chromium salts are turned to
Bordeaux.
H
‘
I‘ ‘
_
.
i
The heavy 'metal complex compound corre
10
sponds to the following formula:
.
commences immediately, and after some time
there is obtained a clear orange yellow solution. 15
;
H \C_N=N
%
The dyestuff soon begins to crystallize, and by
N—N
__Cr
..1
20
- Example 7
3.2 parts by Weight of resorcinol are dissolved in
“100parts by weight of “water, and the solution is
weakly’ acidi?ed with hydrochloric acid. 'To the
25 solution-there‘is'added a diazo solution'prepared
‘ from 3lpartsiby‘weight of amin'ot‘etrazole contain;
ing water of crystallization, 2 parts by weight of
sodium nitrite, 100 parts by weight of water and
5 parts by Weight of concentrated‘hydrochloric
30 acid.
sodium sulfonate are dissolved in 120 parts by
Weight of water, and the solution is acidi?ed with
hydrochloric acid until acid to Congo red. To
the acid suspension 'o'fthe aminonaphthol sul
fonic acid there is ‘added in one portion a diazo
solution preparedfrom 3 parts by weight of am
inotetrazole containing water of crystallization
and 2 parts byweight of sodium nitrite in 100
parts by weight of water and 5 parts by Weight
of concentrated" hydrochloric acid. Coupling
0H
N-NH
>
Coupling commences immediately, and the
the addition of common salt its separation is com
pleted; It is isolated in the usual manner and
again dissolved in 100 parts by weight of water
with 10 to 15 parts by weight of sodium carbonate.
To the solution there is added the tetrazo solution
prepared in the usual manner from 3.6 parts by
weight of dianisidine and 2 parts by weight of‘
sodium nitrite. ‘ The coupling is accelerated by
the addition of pyridine.
The dyestuff is iso 25
lated by salting out andrpressing; it dyes cotton
greenish-dark blue shades, which by after-cop-l
pering become fast to light and washing .
' ,
The heavy:- metal complex compound corre
sponds to the following ,formula:
dyestuff has soon completely separated in‘ the
form of a yellow crystal powder.
When the cou
pling is complete, the dyestu? is brought into’
solution by the addition of'15-20 parts by weight
35 of's'odium carbonate,land the coupling product is
35
coupled with a tetrazo solutionlobtained by tetra
zotizing 1.34 parts by weighti'of benzidine. The
coupling is’ accelerated by thev addition of pyri
dine. The dyestuff is isolated by salting out and
40
40 pressing; it dyes cotton reddish-brown shades
which by after-coppering become‘ fast to light
and washing.
‘
The heavy. metal complex compound corre
sponds to the following formula:
45
45
ll
N¢
7'
.N___
(1)
50
‘
’
Hit
N=N
50
N
Dyestuffs exhibiting similar properties are ob
tainedby substitutingthe dianisidine by benzi
dine, benzidine-o.o'-dicarboxyli'c' acid or de
rivatives of benzidine other than dianisidine, or
by 4.4’-diaminodiphenylamine or other deriva
tives of the benzene or naphthalene series con
taining two diazotizable amino groups.
60
60
Example 9
The dyestu? described in' Example 7 prepared
\.
u
.
\
.
a
%
-:
by coupling in acid solution ‘one molecular propor
65
tion of aminotetrazole and one molecular propor-
,
tion of 2-amino-5-naphthol-7~sulfonic acid is
' coupled in solution, alkaline with sodium carbon
Dyestuffs exhibiting similar properties‘are ob—‘
tained by substituting the benzidine by its sub
stitution products, such as dianisidine, by 4,4’
diaminodiphenylurea or derivatives thereof orv by
diaminodiphenylarnine or other diazo compo
nents of the benzene series containing two diazo
tizable amino groups.
ate, with the coupling product from one molec
uiar porportion of tetrazotized benzidine and one 70
molecular proportion of salicylic acid, if desired
with the addition of pyridine. The dyestuif thus
obtained dyes cotton blackish-brown shades
which by after-treating with copper sulfate solu
tion become fast to light and Washing.
75
4
2,095,484.
The heavy metal complex compound corre
sponds to the following formula:
ing.
In its free state the copper complex com
pound corresponds to the following formula:
10
15
15
20
4 parts by weight of aminotriazole carboxylic 25
acid are dissolved in 250 parts by weight of water
with the aid of soda, 2 parts by weight of sodium
By combining the dyestuif from one molecular
proportion of diazotized aminotetrazole and one
molecular proportion of resorcinol with the di
azoazo compound from one molecular proportion
of tetrazotized benzidine and one molecular pro
portion of salicyclic acid there is obtained a dye
35 stu?? dyeing cotton yellowish-brown shades which
by after-coppering become fast to light and wash
ing.
then poured into a solution of 4 parts by weight
of salicylic acid in 300 parts by weight of water,
the said solution containing soda in such a quan
tity that the coupling mixture is reacting alkaline
to soda. The yellow monazodyestu? yields when
dyed on wool and after-treated with a chromium
salt yellowish brown shades.
The chromium complex compound corresponds
Example 10
40
nitrite are added and after cooling the solution
is acidi?ed with aqueous diluted nitric acid. The
diazo solution is allowed to stand for 30 minutes,
to the following formula:
40
3.8 parts by weight of aminotriazole carboxylic
acid are dissolved in 100 parts by weight of water
with the aid of ammonia, 2 parts by weight of
sodium nitrite are added, and while cooling the
45 solution is acidi?ed with hydrochloric acid. The
diazo solution obtained is brought into a sus
pension of an equivalent quantity of 2-amino
5-hydroxynaphthalene-7-sulfonic acid in 800
parts by weight of ice water, the said suspension
Weakly reacting acid to Congo. When the cou
pling is complete, the monoazodyestuff is isolated
in the usual manner and dissolved with the aid of
15 parts by weight of soda in a mixture of 100
Example 12
4 parts by weight of aminotriazole carboxylic
acid are diazotized as described in Example 11
and coupled in a mineral acid solution with 4.6 50
parts by weight of 8-amino-quinaldine. The
yellow monoazodyestuif is dissolved in water with
the aid of ammonia, 2 parts by weight of sodium
parts by weight of pyridine and 100 parts by
nitrite are added and after this the solution is
Weight of water. Into this solution there is slow
ly dropped in at 30-4=0° C. the diazo solution pre
pared in the usual manner from the equivalent
acidi?ed with dilute aqueous hydrochloric acid.
quantity of dianisidine, then the temperature is
The diazo compound isolated in the usual manner
is coupled in a soda-alkaline medium in the pres
ence of pyridine with the calculated quantity of
elevated to 60° C. and kept at this temperature
for several hours While stirring. The tetrakisazo
dyestuff formed is salted out, ?ltered and dried.
The dyestuff dyes cotton from a Glauber’s salt
fonic acid. The dyestu? dyes cotton from a 60
Glauber’s salt bath violet shades, which on after
treating with copper salts are turned to a clear
greenish blue of good fastness to washing.
bath navy blue shades, which by after-treatment
65 with copper salts become fast to light and wash
2 - phenylamino-5-hydroxynaphthalene - '7 - sul
The copper complex compound corresponds to
the following formula:
OH.
70
HO OO-O-NH
NIii-O Tau
75
75
5
£095,484
coupling positions, bearing attached to the other
“In the following table there are given some fur‘
ther combinations and the‘shade of the copper coupling position the radical of a diazotized
' heterocyclic amine containing in a ?ve-membered
compound on cotton:
V
_
shadecomp
oithleex
copper
Dyestu?
compound on
-
v(1)
cotton
I-acid (- dianisidine -)
10
I-acid
'aminotriazole
(2)
I-acid (- dlanisidine —)
aminomethyltriazole
(3)
15
I-acid I
Navy blue.
m-phenylendiamine <- benzidine-mor’i —) m-p_hen_yldlcarboxylicacid
azole
resorcinol <~lbenzidine-o,0’-_ —-> resorcinal
Brown.
dicarboxylic acid
20
aminotriazole
aminotriazole
2, 4-toluylen- (- benzidine-o,o’- —) 2, 4-tol_uylen-
(5)
diarmine
dicarboxylic acid
aminotriazole
1-methyl-3-
7
Brown.
diarmine'
aminotriazole
(6)
15
aminotri
‘
25
Brown.
endiamnie
aminotriazole
i
V10
‘
amlnomethyltriazole
7
(4)
Deep navy blue
aminotriazole
{-
V
.
Blackish brown. 25
benzidine-o,o'-_ -—> I-acid
phenyl-5-pyrazolone dicarboxylic acid
7
-
'
'
‘
'
aminotrlazole
carboxylic acid
(7)
aminotetrazole ——> diacetoacetic- <— aminotetrazole
30
o-tolidine
(3)
m-phenylendiamine
Yellow.
30
_
dianisidiner —> m-phenylen-
Blackishbrown.
diamine
aminotetrazole
The heavy metal complex , compounds when
prepared in substance generally are water-insol
uble substances'suitable as pigments.’
We claim:
’
’
aminotetrazole
'
nucleus thegrouping
40 stu?s which are derived from heterocyclic amines
as diazotization components containing in a ?ve
membered carbon and nitrogen containing heter
ocyclic nucleus the grouping
V ' '
'
__N=(l3_NH_
N112
7'
LI-Ieavy metal complex compounds of azodye
35
carbon and nitrogen containing heterocyclic
in which group the amino group is capable of
undergoing diazotization, and R” stands for a
member selected from the group consisting of R’
and another azodyestu? coupling component.
3.-Copper complex compounds of the azodye-.
stuff of the general formula:
I
Y
50
in which group the amino group'is capable of
undergoing diazotization; yielding when prepared
' on the ?ber generally Various shades of good fast
ness properties.
'
_
l
l
2. Heavy metal complex compounds of azodye
55
60
stuffs of the general formula:
'
'
'
>
:
wherein R’ stands for the radical of an azodye;
stuff component with two coupling, positions,
bearing attached to the other coupling position
the radical of a diazotized heterocyclic amine
containing in a ?ve-membered carbon and nitro
gen containing heterocyclic nucleus the grouping
in which group the amino group is capable of
undergoing diazotization, and R" stands for a 60
wherein X represents a member selected from the 7 member selected from the group consisting of R’
group consisting of a carbon-carbon linkage, an and another azodyestuff coupling component,
oxygen atom, a sulfur atom, an imino group and
Y stands for a member selected from the group
the group —NI-I—CO-—NH—, R stands for a
consisting of hydrogen, the 'carboxylic acid group
radical of" the benzene, series, bearing the azo
and‘an alkoxy group;
group in para-position to X, R’ stands‘ for'the
radical of an azodyestuff component with two
'
CARL TAUBE.
'
-
-
‘
JOHANN HEINRICH HELBERGER;
‘
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