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Патент USA US3078276

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United grates
Ii,d78,2% .
Patented Feb. 19, 19%3
2
1
alkoxy-l-aminobenzene unsubstituted in the 4-position,
3,078,266
such as Z-methoxy-l-aminobenzene, Z-methoxy-S-methyl
‘l-aminobenzene, 2:5-dimethoxy- or 2:5-diethoxy-1-amino
Walter Hanhart, Riehen, Switzerland, assignor to Ciha
benzene or the like, or with a 2-alkoxy- or Z-carboxy
methoxy-l-aminonaphthalene derivative, such as a 2
POLYAZG-DYESTUFFS
Limited, Basel, Switzerland, a Swiss ?rm
No Drawing. Filed July 20, 1959, Ser. No. 828,037
Claims priority, application Switzerland Aug. 6, 1958
methoxy-l-amino-naphthalenc monosulfonic acid unsub
stituted in the 4-position. As diazo-components to be
coupled with such coupling components for making the
starting components of the formula R-NHZ there may
8 Claims. (Cl. 260-446)
This invention provides valuable new polyazo~dyestuifs
of the general formula
(1)
O O-NH
10
be mentioned:
(a) Simple benzene or naphthalene derivatives: amino
salicylic acid, aminobenzoic acids, aminobenzene-ortho-,
CO
-meta- or -para-sulfonic acid, l-aminobenezene-Z:S-disul
fonic acid, 4-chloro-l-aminobenzene-2-sulfonic acid, and
CO-Né
in which R represents the radical of a (haze-component
also nitro- or cholro-anilines, 4-amino-4’-acetylaminodi
group, and also provides complex heavy metal compounds,
especially complex copper compounds, of the poiyazo~
pling component containing a diazotizable amino group,
such as 3-methyl-aniline, 1-aminonaphtha1ene-6- or -7-sul
fonic acid and also the coupling components mentioned
above that contain amino groups, and also those ob
tainable by coupling a diazo-compound of a monoacylated
diamine with any desired coupling component and sub
sequently hydrolyzing the acylamino group to form a
.free amino group.
Useful amino-azo-dyest-uffs of the Formula 2 can
containing at least one azo linkage, and which radical 15 phenyl-S-sulfonic acid, l-aminonaphthalene-S :o-disulfonic
acid, 2-aminonaphthalene-4:S-disulfonic acid or dehydro
contains in a position vicinal to the -N:N—-A—- group
thiotoluidine mon0~ or di-sulfonic acids; (b) Amines con
ing a group capable of taking part in the formation of
taining azo linkages, such as amino-azobenzeue mono- or
heavy metal complexes, and A represents the radical
di~sulfonic acid, and those obtainable by coupling a diazo
of a hydroxynaphthalene sulfonic acid bound to the
compound of an amine mentioned under (a) with a cow
R—N=N-- group in a position vicinal to the hydroxyl
dyestuif of the above formula.
The invention also provides a Process for the manu
facture of the dyestuffs of the above general Formula
1, wherein barbituric acid is coupled With a diazo
compound of an amino-polyazo-dyestuff of the general
formula
(2)
be obtained by coupling a tetrazotized diamine, which
or of a complex heavy metal compound of such dye— ’
stuff, in which formula R represents the radical of a
diam-component containing at least one azo linkage,
and which radical contains in a position vicinal to the
contains in a position vicinal to the diazo-group a group
ing capable of taking part in the formation of metal
complexes, for example, by coupling tetrazotized 4:4'-di—
amino-3:3'-dimethoxy-diphenyl, on the one hand, with an
—N=N—A— grouping a group capable of taking part in
the formation of heavy metal complexes, and A represents
aminonaphthol sulfonic acid capable of coupling in a
position vicinal to the hydroxyl group and, on the other,
With any desired coupling component, and advantageous
ly one capable of forming metal complexes.
As diazo-components to be coupled with the aforesaid
the radical of a hydroxynaphthalene sulfonic acid bound
to the azo linkage in a position vicinal to the hydroxyl
group, and which radical advantageously contains the
—-NH2 group bound directly to the naphthalene nucleus.
coupling components for making the starting compounds
The metal-free dyestuffs of the Formula 2 used as
starting materials can be obtained by coupling an amino
naphthol sulfonic acid (for example, Z-amino-S-hydroxy
naphthalene-7-sulfonic acid, Z-amino-é-hydroxynaphtha
lene-8-sulfonic acid, Z-amino-8-hydroxynaphthalene-G-sul
fonic acid or 1-amino-8-hydroxynaphthalene-3:6- or -4:6
disulfonic acid) in a position vicinal to the hydroxyl
group with a diazo-compound of an amino-azo-dyestuif
of the formula R—NH2, Which contains in a position
vicinal to the diazo-group a grouping capable of taking
part in the formation of metal complexes, for example,
a carboxyl group or a hydroxyl group that may be etheri
?ed.
Instead of the aforesaid aminonaphthlo sulfonic
acids, which contain the amino group bound directly to
of the formula R-NH2, there may also be used the com
plex metal compounds thereof which are obtainable by
the metallization of monoazodyestufr's obtainable, for ex
45
ample, from 1-aminophenyl~3-methyl-5-pyrazolones, 1
aminophenyl-3-carboxy-5-pyrazolones, l-aminostilbenyl
B-methyl-S-pyrazolone-Z’:2"-disulfonic acid and diazo
tized ortho-arninophenols and sulfonic acids thereof or
diazotized ortho-aminobenzoic acids and sulfonic acids
thereof.
The dyestuffs of the Formula 2 can be made by the
usual known methods. The initial components are
advantageously coupled with the aminonaphthol sulfonic
acids in an alkaline medium. Before or preferably after
the diazotization and coupling of the amino-azo-dye
stuffs so obtained, of which a large number is known
the naphthalene nucleus, there may be used aminonaphthol
with barbituric acid, they may be converted into complex
“sulfonic acids which contain this diazotizable amino group
metal compounds thereof. As agents yielding metal there
in an external nucleus, for example, in a benzoyl radical.
may be used, for example, agents yielding nickel but
As examples of such aminonaphthol sulfonic acids there 60 preferably agents yielding copper. The treatment with
may be mentioned 2-(4'-aminophenylamino)~5-hydroxy
the agent yielding metal is advantageously carried out
naphthalene-7-sulfonic acid and more especially 2-(4'
in
such manner that a complex metal compound of an
aminobenzoylamino) - 5 - hydroxynaphthalene-7-sulfonic
ortho-carboxy-ortho'-hydroxy- or ortho : ortho’edihydroxy
As diazotized amino-azo-dyestuffs there may be men~ 65 azo-dyestuff is formed, that is to say, in such manner that
any alkoxy group present in ortho-position to the axe
tioned diam-compounds of amino-monoazo- as well as
linkage is split up and one atom of metal is bound in
amino~disazo-dyestuiis, which can be made by the usual
- acid.
methods, for example, by coupling any desired diazo
complex union, for example, with one ortho:ortho'-dihy
droxy-azo-grouping or one ortho-hydroxy-ortho'-carboxy
compound with a coupling component containing a free
amino group and containing in a position Vicinal to the 70 azo-grouping.
'free amino group a grouping capable of taking part in
. the formation ofmetal complexes,.for example, with a 2
The treatment with the agent yielding metal is, there
fore to be carried out in such manner that an ortho:ortho'
3,078,266
3
4
dihydroxy-azo-copper complex is formed, when the metal
sulfonic acid capable of coupling in a position vicinal
lizable grouping is an ortho:ortho'-dihydroxy-azo- or
to the hydroxyl group and bound directly to the azo‘
ortho—hydroxy-ortho’-alkoxy-azo-grouping. As is known
linkage, and, if desired, the polyazo-dyestutfs so obtained
is converted into a complex heavy metal compound
this reaction takes place more easily with an ortho:ortho’
dihydroxy-azo-grouping than with an ortho-hydroxy
thereof.
For making the dyestuffs of the Formula 4 there may
ortho’-alkoxy-azo-grouping, so that in the latter case a
longer period of reaction and/ or a higher temperature is
be used as diazo-components the amino naphthol sul
required. The metallization is carried out, ‘for example,
fonic acids mentioned above for use as coupling com
ponents in making the dyestuffs of the Formula 2. As
aqueous medium. The dyestuffs can also be metallized 10 amino-azo-dyestutfs to be coupled with the dyestuffs of
the Formula 4 there are used in this modi?cation of the
by the known method in which the metallization is carried
process the products obtainable by the methods described
out in ‘an aqueous medium advantageously for several
above for making the compounds of the formula R-NHg
hours in the vicinity of 100° C. with the use of a nickel
with a salt of divalent copper or nickel in a weakly acid
The polyazo-dyestut‘fs of this invention are suitable
or copper-tetrammine complex in the presence or absence
of an excess of amine or ammonia. Of special advantage 15 for dyeing or printing a very wide variety of materials,
for example, those of animal origin, such as Wool, silk
in some of these cases is the process of Patent No.
or leather, and especially for dyeing or printing cellulosic
2,536,957, which is carried out in the presence of a hy
droxyalkylamine, especially ethanolamine, or a copper
materials, such as cotton, linen, arti?cial silk or staple
?bers of regenerated cellulose. Those dyestuffs that con
complex derived therefrom.
The dyestuffs of the general Formula 2 which contain 20 tain no heavy metal or contain a metallizable group may
in a position vicinal to the azo linkage connecting R with
A an alkoxy group bound to a naphthalene radical, for
be treated on the ?ber or in the dyebath with an agent
yielding a heavy metal, advantageously an agent yielding
example, dyestuffs of which the radical R in the Formula
copper.
In some cases especially valuable dyeings are obtained
2 has the formula
by using the process in which a dyeing or print produced
OCH:
with the metal-free dyestu? is after-treated with an aque~
ous solution which contains a water-soluble, and espe
cially complex, copper compound and a basic formalde
hyde condensation product of a compound containing at
30 least once an atomic grouping of the formula
H03
in which R1 represents the radical of any desired diazo
component, are in‘ general advantageously coppered with
copper sulfate in the presence of an alkali metal acetate.
On the other hand, those dyestulfs which contain at 35
the aforesaid position in the molecule an alkoxybenzene
for example, dicyandiamide or dicyandiamidine, or a
radical, for example, a radical of the formula
compound, for example, cyanamide, that is easily con
40
vertible into a compound containing such an atomic
grouping. Such a process is described, for example, in
Patent No. 2,526,106.
The dyeings produced with the new dyestuffs in the
manner described above are usually distinguished by their
good properties of wet fastness, and especially their very
45 good fastness to light and good capacity for being dis
charged.
The following examples illustrate the invention, the
parts and percentages being by weight:
Example 1
50
‘are advantageously converted into the ortho:ortho’-di
6.2 parts of the disazo-dyestutf of the formula
‘hydroxy-copper complex by means of a copper-tetram
mine sulfate.
OCH;
ml)
The metalliferous dyestuffs so obtained are also
largely known and correspond to the Formula 2.
55
The diazo-compounds obtained from the amino-azo
dyestuffs of the Formula 2 or their complex metal
H3
H038
NH:
compounds are coupled with barbituric acid to form
the dyestu?s of the Formula 1 advantageously in
H035
a weakly alkaline medium. The dyestuffs so obtained, 60
which contain no heavy metal in complex union, can be
are dissolved in 100 parts of warm water in the form of
metallized, for example, by the methods described above
the sodium salt. The solution is cooled to 5-10° C., 0.7
for metallizing the starting dyestuffs of the Formula 2.
part of sodium nitrite is added dissolved in water, and
The dyestn?s of this invention, that have the Formula
then 4 parts of hydrochloric acid of 30% strength are
1, can also be made by a modi?cation of the process de
added, diluted with a small amount of water, the whole
scribed above, wherein a diazotized amino-azo-dyestuff,
is
stirred for a few hours, while cooling, and then cou—
which contains in a position vicinal to the diazo group a
pling is carried out with a solution of 1.3 parts of bar
grouping capable of taking part in the formation of metal
'bituric acid rendered alkaline with sodium carbonate.
complexes, for example, a hydroxyl, alkoxy or carboxyl
When the coupling is complete 5 parts of sodium chlo
group, is coupled with a monoazo-dyestuff of the formula
70 ride are added for every 100 parts by volume of solu
QN=N~
(4)
o O-NH
x-N=N-o
oo
o O-N
N=N-—
tion, and the precipitated dyestuff is ?ltered off. By heat
ing the precipitate for several hours in a weak acetic acid
solution with copper acetate the complex copper com
pound is made in known manner. The latter compound
in which X represents the radicalof a hydroxynaphthalene 75 -is dried, and is a green-black powder which dissolves in
3,078,266
5
6
the dyestuffs of the formulae given in column I of the
following table, in which are given in columnlI theltints
of the dyeings produced on cotton with the ?nished
water with a green coloration, and yields green dyeings '
on cotton or viscose.
Similar dyestuffs are obtained by using, instead of the
dyestu? obtained from ,1-amino-3-methylbenzene, one of
cupriferous barbituric acid-dyestuff.
I
S 03H
1 .......... ._
C1-—~
II
0 CH3
-N=N
IiIO
N=i '
Blziish green.
HO: S
—NHz
H 0 3%
S 0 3H
2 .......... ..
(1) C H:
—N==N
HO
—N=N
‘DO.
I H O 3 3‘
“NH:
1
S 03H
g 03H
-
? 03H
0 OH:
3 .......... -. HaC-®—N=N——
OH
—N=N
‘Do.
H 03 S
,
NH:
H O: s
'
S|02H '
v
0 CH3
4 .......... .. HzCGOHN—-C>—®—N=N—
HO
N=N ‘ '
‘H 03s
'
Do.
-NHz
i
H 038
N
/ \
5 .......... ..
O CHa
1
C
H30
S
——N=N—-
/
HO
Green.
—-N=N
SOSH
HOaS
’
—NH:
I
I
S10 3H
H 025
0 CH3
o .......... -. C>—N=N
HO
—~N=H
D0.
HOaS
NHC O—O—NH2
H038
O CH;
7
......... ..»_~
v G
-N=N
H0
—-N=N
Biuish green.
HOaS
NH:
H 033
(i') 6H3‘
8 __________ ._
‘ -N=N
HO
—N==N
8 OzNHz
Do.
H035
—NH2
8 OaH
O OH;
9 .......... .- Cl-—®—N=N
HO
N=N
HOaS
Do.
-Nm
' 3,07 8,268
'
7
8
TABLE-Continued
I
II
C|>CHa
10 _________ __ 01330 OHNON=N
H0
—-—N=N
Do.
H038
-NH:
HOaIS
(130E;
11 ......... .. O:N—C>~N=N
H0
N:
Green.
H038
-—NH:
H035
H0315
OCH:
12......... .. ®—COHN—C>—N=N
H0
N=N
Bluish green.
Hoes
'
OCH:
13 ......... _- 041:»:
Hols
H0
N=N
SIOsH
HOaS
dOzH
Do.
—NH2
01‘
Example 2
35 with a little water, are added, and the whole is stirred in
_
the cold for a few hours. Coupling is then carried out
6-7 Parts of the dlsazo'dyestu? of the formula
0
|o
0H
‘
'
H0
-—-NH:
OCH
:
N=N
N:
HOE
HO
with 1.3 parts of barbituric acid in a solution rendered
alkaline
with sodium
carbonate.
When. the coupling is
.
. .
.
?nished the preclpitated trisazo-dyestuff 1s ?ltered off, and
40 converted in acetic acid solution into its complex copper
.
compound by heating it with copper acetate in known
NHa
manner. When dry, the copper complex compound is a
green-black powder which dissolves in water with a green
-
H018
coloration, and yields green dyeings on cotton or viscose,
are dissolved in the form of the sodium salt in 75 parts
of warm water. The solution is cooled to 5—10° C., 0.7
part of sodium nitrite, dissolved in water, is added, and
then 4 parts of hydrochloric acid of 30% strength, diluted
45 which are fast to washing when after-treated with copper
salts.
Similar dyestuffs are obtained by using, instead of the
starting dyestutt of the above formula, the following
disazo-dyestuffs.
coon’
OCH:
110
l
H038
NH:
hour
OCH!
HO
NHC oQ-Nm
son:
(IIOOH
OCH:
H0
-s
"8,078,266
10
Example 3
9 parts of the disazo-idyestu?' ofithe formula
611-"
’ moo
HO
OOH;
,NH:
H038
H033
SOaH
are dissolved in the form of the sodium salt in 450 parts
of hot water. The solution is then cooled» with ice to
about 5° C., 0.7 part of sodium nitrite, dissolved in a 1
and “
1108s
on
moo
_
00H,
__
small amount of water, is added, and diazotization is
brought about by adding 5 parts of hydrochloric acid of
30% strength.
The whole is stirred for a few hours,
'
,
while cooling, and then coupling is carried out with 1.3
parts of barbituric acid in a ‘solution rendered alkaline 20
with sodium carbonate. When the coupling is complete
the trisazo-dycstu? formed is precipitated by the addi~
Example 4
7.9 ‘parts of the trisazo-dyestuff of ‘the formula
tion of sodium chloride, the dyestuff is ?ltered oif and
SOaH
'
‘
then converted into its complex copper compound in
known manner by heating it with an ammoniacal solu
' '
Hots
NH:
0.7 part of sodium nitrite in aqueous solution and 4.5
parts of hydrochloric acid of 30% strength diluted with
a little water are added, and the whole is stirred for a
pound, when dry, is a blackish powder which dissolves in
'
‘H3
are dissolved in the form of the sodium-salt in 100 parts
few hours in the cold. Coupling with 1.3 partsiof bar
water to give a dull blue coloration. It dyes‘, cotton or
grey tints.
OOH;
35 of hot water-and cooled by the addition of ice to 5-10“ C.
tion of copper oxide, if desired, ‘in the presence of a
small amount of pyridine. The complex'copper com
viscose
1103s
bituric acid is then carried out in a solution rendered
'
alkaline with sodiumcarbonate. When the coupling is
?nished the precipitated‘ dyestulf is ?ltered off, and con
verted into its complex copper compound in known
Grey-dyeing complex copper compounds are obtained
in a similar manner from the dyestuffs of the formulae
manner by heating it with an ammoniacal solution of
HO3|S
on
113ml)
o'orn
‘ H03s-H0
NE:
45 copper oxide.
The complex copper compound, when
dry, is a blackish powder which dissolves in water with
aigreen coloration, and dyes cotton blackish olive-grey
tints.
.
Similar dyestuffs are obtained by using as starting ma
Hogs
I
i
50
terials the following dyestuffs:
(I) C H3
H0
N=N—
HOaS—
Blackish oliveegreen.
—-NH:
Olive-green.
3,078,266
11
TABLE--Continued
can;
4 .... -. ©~N=N
—N=N—
soar:
B0311
—N=NON=N—
on!
03H'
'7
-‘
|
.
,
I
7
'
'
V Greyish olive.
Nlit;
"
~
7
‘
" “
' no
'
-N=N
a
-
‘
v_
(‘>033
_
‘
1103's’
e031;
T
H0
N=N
1"
403E
12
a
Green. ‘
1103s
—NHi
‘H018
'
'
'
.
l
v
6 ---
' $11,
‘
Hols
SOaH
---NH:
03H
slom
(‘mm
7 ____ ..
~N=N
-—N=N-—
‘
otn'
'
110
N=1.
Blucklsh olive-green.
HOaS ,
s om
s 091
0 OH:
s 01H
NH:
s 031!
H0
s OaH
.
OCH:
9.--..- H018
:N
-N=N-—
(|)H
N=N
Ha
Green.
H018
HOaS
NH:
s 03H
8 0:11
0 OH:
10.....
H0
N= QN=N
N=N
H;
HOzS
OH
Do
‘
NH:
I
03H
H0=s ‘
11-_._.
‘
Hols
(IJCHa
)- =N~©—N=N
.‘I H
VH0
N: _
CH:
Do
HOsS-
NH;
S 0311
In the case of dyestuffs derived from l-amino-Z-methoxynaphthalene sulfonioacids from the coppering is
with the monoazo-dyestu? of the formula
advantageously carried out in an acetic acid’medjum.
_
The sequence of the operations can generally be varied, ‘65
for example, dyestu? No. 1 in the table can equally well " ‘
HO
'
be prepared by coupling the disaz'o-dyestu? of the for-
1
mula
'
~
.
B0111
'
v i
V
(JO-NH
or by carrying; out the coppering§before the ?nal coupling
75 operation with barbituric acid.
3,078,266
'
.
_
I3
.
aminonaphthalene-6-su1fonic acid.
12.2 parts of the disazo-dyestuif of the formula
‘
$03K
t4
disulfonic acid, 1-aminonaphthalene-4~sulfonic acid or 2
Example 5
OCH:
OH
- _
are dissolved as the sodium salt in 120 parts of water.
Example 6
At 54.6‘, C' an aqueous ‘Solution “of 0'7 Part of sodium
12.3 parts of the trisazo-dyestuif of the formula
0 CH3
COOH
. '
1
"O
' Y HOgSON=N-O§
H035
nitrite and 3.5
'are dissolved as the sodium salt in 180 parts of warm
of hydrochloric'acid of 30% strength, 25‘ Water. ‘The solution is cooled to 540° C. and 0.7 part
of sodium nitrite is added as an aqueous solution and 4
diluted with a littlewater, are added. The diazotization
parts of hydrochloric acid of 30% strength, diluted with
?nishes rapidlyf‘Coupling ‘with 1.3 parts of barbituric
. a little water, are added.
acid is then carriedout in a solution rendered alkaline
with sodium carbonate, while cooling. The trisazo-dye
stuff precipitates completely. It is ?ltered off and con
verted into its complex copper compound in known man
ner by heating it in a weakly acetic acid solution with
copper acetate. The dyestu? dissolves in water with a
green coloration and yields green dyein'gs on cotton or
viscose.
I
The whole is stirred for a few
hours, while cooling, and coupling with 1.3 parts of bar
‘ bituric acid is then carried out in a solution rendered al
kaline with sodium carbonate. The precipitated dyestuff
is ?ltered off, and converted into its complex copper com
pound by heating it in acetic acid solution with copper
acetate. The complex copper compound, when dry, is a
dark green powder which dissolves in water with a. green
coloration and yields olive-green dyeings on cotton.
Similar dyestuffs, which dye vegetable ?bers green
tints, are obtained by using trisazo-dyestu?s of the for
’
Similar dyestu?s‘ are obtained by using instead of 1-)
aminonaphthalene-ll: 8-disu1fonic acid to form the triazole,
mulae
COOH
50311
$0011
/ 00-N-O
I
I
can:
l
N=N
c
l
o
S0311
_
Y
,
.
’
coon
I
(1) CH3
'
o O——N——
-N=N-o§ ‘
—N='N
~
on
N=N——
\
HOaS-—
—-NH2
O=N
SOQH
H2
another aminonaphthalene sulfonic acid, such as l-amino-
‘naphthalene-3zd-disulfonic acid, 2-aminonaphtha1ene-5z7SOQH
‘
C0011
l
SOaH
Example 7
116 parts of ma trisazwdyesm? of the formula
OOH;
H
3,078,266
16
are dissolved as the sodium salt in 200 parts of water.
in which n and m each is a positive whole number up to
0.7 part of sodium nitrite and 4 parts of hydrochloric acid
2, m+n is at most 3, A is a radical selected from the
group consisting of
of 30% strength, diluted with a little water, are added,
and the whole is stirred in the cold for a few hours
on
'
‘
Coupling with 1.3 parts of bartituric acid is then carried 5
out in a solution rendered alkaline with sodium carbonate,
and the dyestuff formed is precipitated by adding 10 parts ,
p
of sodium chloride for every 100‘ parts by volume of liq-
H035
_
_
‘
uor. By heating the precipitate in a weekly acetic acid
solution with copper acetate the complex copper com- 10
‘
and
pound is prepared in known manner. When dry it is a
dark green powder which dissolves in water with a green
coloration and yields green dyeings on cotton or viscose.
0H
Example 8
1.84 parts of 4:4'-diaminodipheny1-are tetrazotized, then
coupled in alkaline solution on one side with 1.8 parts
I
of 1-hydroxybenzene-Z-sulfonic acid and then in neutral
‘
or weakly acid solution with ‘2.5- parts of 1-amino-21 .
_ ,
R1 15 a Member Selected froth the group consisting of a
methoxynaphthalene-G-sulfonic acid. When the coupling 20 benzene, naphthalene_ and blphenylef‘lefadlcal, R2 15 a
is ?nished the disazo-dyestufr' obtained is isolated, then di-
- - member Select‘? from the group 60115150118 of ‘3 b61116“,
azotized, and coupled in alkaline solution with 2.4 parts
of 2-amino-5-hydroxynaphthalene-7-sulfonic acid.
naphthalene’ blphenylenel
The
V
trisazo-dyestuif is precipitated by the addition of sodium
'''
_
“QNH_COO
chloride, then dissolved by the addition of 8 parts by 25
-
volume of a 2 N-solution of sodium hydroxide, and di-
Z11
azotized after the addition of sodium nitrite and hydro~
chloric acid and a little ice in the usual manner.
a alt-<3
The
product is then coupled with 1.3 parts of barbituric acid
_o\
in a solution rendered alkaline with sodium carbonate. 30
C=N
The complex copper compound of the resulting dyestuif
of the formula
s 03H
'
('33,
0 OH;
O O-N
is obtained by heating the dyestuif for several hours with
and
copper acetate in a weakly acetic acid solution. The cop
per compound is ?ltered off and dried, and is then a black
powder which dissolves in concentrated sulfuric acid with
coloration.
a blackish brown
It dyescoloration
vegetable and
?bersin olive-green
water withtints
a green
that 45
are fast to light.
Example 9
OH
.
/(h-N-<3-GH=OH~O
__O/_
\C_N
43
H:
radical, and R3 is a member selected from the group con
'100 parts of cotton are entered at 40° C. into a dye- 50 sisting of a benzene, a biphenylene, a stilbene, a benzoyl
bath which contains in 3000 parts of water 1 part of the
anilino, a dihydrothiotoluidine, an acetic acid anilide and
dyestu? obtainable as described in the ?rst paragraph of
a naphthalene radical, and which dyestutf contains at least
Example 1. Dyeing is carried on for half an hour while
two sulfonic acid groups.
raising the temperature of 90° C., then 30 parts of
2. Complex copper compounds of the polyazo-dyestuffs
crystalline sodium sulfate are added, and dyeing is con- 55 of the formula
tinued for a further 1/2 hour at 90-95 ‘’ C. The cotton is 65 in which n=2, m=l and R2 represents aiipyrazolone
then rinsed and dried. There is obtained a green dyeing
radical which is bound in the 4-position to the
of very good iastness to light.
R3—N=N=group and in the l-positron through‘ a
What is claimed is:
; '
1. A complex copper compound of polyazo-dyestu?s
of the formula
phenylene group to the —-N=N.——R1=group_, _R1 being
a naphthalene and R3 a benzene radical containing a sul
ionic acid group.
3,078,268
1 '3'
18
3. Complex copper compounds of the polyazo-dyestuffs
of the formula
HO
-NfEt
S 0 3H
in which n is a whole number up to 2, R represents a
benzene nucleus and R1 21 l-phenyl S-pyrazolone radical
bound to R—N=N— in 4 position and to the other azo l5
linkage through the phenyl substituent in its l-position.
4. The complex copper compound of the formula
O O-NH
SOaH
5. The complex copper compound of the formula
8. The complex copper compound of the formula
803B
5
113
803K
No references cited.
CO—NH
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3,0783%
February 19‘ 1963
Walter Hanhart
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
Column lv line 541:‘z for "aminonaphthlo" read —- aminonaphthol
——;column 2v line lélv for "cholro-anilines" read —~ chloro
anilines ——; column 11,, line 63,, strike out "from"; columns 13
and lélq at the bottom of the pagey extreme left-hand portion
of theformula should appear as shown below instead of as in
the patent:
S0311
SO3H
column 15, line 5q for "bartituric" read —— barbituric -—;
line 9, for "weekly" read —— weakly —~; columns 17 and 18,1
formula in claim 40 the extreme right~hand portion of the
formula should appear as shown below instead of as in the
patent:
same columns 17 and 189 the formula of claim 6 should appear
as vshown below instead of as in the patent:
S0311
CO-NH
:N
H038
N=N
N:N
H035
CHv
3
503a
/
N:N—CI-I\CO—NH/co
'
snmavzaa
same'colurgnns 17 and 18, the formula of claim 7 should appear
as shown below instead of as in the patent: '
‘
‘
HOGNSN
:
1103s
CO-NH
/
i
\ -
CO-ON:N~CH
c0
(IO-NH
8031-1
same columns 17 and 18V the formula of claim-"8v sh-ou-l-d app '16 a 1"
as shownloelow instead of as ‘in the patent:
sogn
r
Signed and sealed this 24th day of December 1963,
(SEAL)
Attestf;
ERNEST W. SWIDER
Attesting Officer
EDWINQL. REYNOLDS
Acting Commissioner of Patents
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