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Patented Nov. 26, "1946‘
2,411,646
UNITED STATES PATENT OFFICE
2,411,646
DISAZO DYESTUFFS AND PROCESS OF
MAKING SAME
Walter Anderau, Basel, Switzerland, assignor to
Society of Chemical Industry in Basle, Basel,
Switzerland, a Swiss company
No Drawing. Application August 2, 1943, Serial
No. 497,077. In Switzerland August 21, 1942
18 Claims.
1
A relatively small number of dyestuffs are al
ready known which contain B-hydroxyquinoline
(Cl. 260-155)
2
the same radical as above, with products-of the
general formula
or its substitution products as a component.
However, as far as mono- and disazo-dyestuffs
are concerned, these dyestu?s are intended for
dyeing wool or other animal ?bers or varnishes
and plastic masses if devoid of solubilizing groups.
Recently it has also become known to make use
of 8-hydroxyquinolines for the manufacture‘ of
in an alkaline medium. Diazotised amines of the
substantive dyes, i. e. dyestuffs possessing a?inity 10 benzene and naphthalene series (whose radical is
for vegetable ?bers, such as cotton, linen or rayon
equivalent to the R1 of the ?rst formula) are
from regenerated cellulose. It has been said‘
particularly suitable. These amines may contain
however that only tris- and polyazo-dyestu?fs are
groups which make the substance Water-soluble,
su?iciently substantive. Furthermore clear red
such as sulphonic acid or carboxyl groups, and
shades have not been obtained with the known 15 other substituents. In some cases it is advisable
to use amines containing a grouping which will
lines as components.
form a metallo-complex, in particular a hydroxyl,
It is an object of the present invention to pro
carboxyl, or alkoxy group, or a grouping
vide a series of new valuable dyestu?s containing
only two azo groups and an 8-hydroxyquinoline 20
as component, which are perfectly substantive.
(particularly —-O—CH2—COOH) , for example in
It is a further object of the present invention to
the ortho-position to the amino group to be di
provide dyestuifs capable of forming complex
azotised. Suitable amines are, for example, 2
metal compounds. More particularly the pres
amino-1-methoxy-benzene-4 - sulphonic acid, 2
substantive dyestuffs containing S-hydroxyquino
ent invention provides dyestuffs which are per 25 amin0phenol-4 - sulphonamide, anthranilic acid,
fectly soluble in the form of their normal alkali
2-amino-3-naphthoic acid and 1-amino-2-meth
metal salts, but become substantially insoluble on
y1-5-phenoxy acetic acid. Further examples of
conversion into complex metal‘ compounds, es
such amines can be found in the table given
pecially copper compounds, the said conversion
later.
being preferably carried out in the dyebath as de 30 The linkage X of the above formula should
scribed below. Still more particularly it is an
preferably consist of at least 2 atoms, at least
object of the present invention to provide dye
one of which should be nitrogen and the other
stuffs of the said kind dyeing blue-red to yellow
one, for example, carbon. It may be, in the sim
r'ed shades of good fastness.
' plest case, an acid amine group, e. g.
It has been found that diazo dyes can be pre 35
pared if diazotised amino-azo dyes of the gen
This linkage, however, may also be part of a ring
eral formula:
which acts, for example, on the ortho-a-position
of the naphthalene nucleus, as is the case in the
40 corresponding imidazoles, thiazoles or triazines.
The aryl radical R2 of the above formulas may
belong, for example, to the benzene series and
should preferably have the amino-group to be
diazotised in the para- or meta-position to the
wherein X represents a connecting link contain 45 linkage X.
ing nitrogen which is different from the azo-group
The diazotisation of these amino-azo dyes hav
andR1 and R2 each represent an aryl radical,
ing the formula given at the beginning is best
are coupled with S-hydroxyquinolines and the
undertaken in many cases indirectly by adding an
dyestuffs obtained treated, if desired, with agents
acid such as hydrochloric acid at a suitable tem
which yield metals.
,
'
,
‘
50 perature to a neutral to weakly alkaline solution
The starting products of the above formula are
or suspension of the amino-azo dye containing the
preferably obtained by coupling a'_ diazotised
amine of theformula R1NH2, where R1 represents
necessary amount of sodium nitrite or introducing
the latter solution into the acid.
2,411,646
3
4
which dissolves in water and dilute alkalies to
red solutions and in concentrated sulphuric acid
According to the present process this diazo- ,
' tised amino-azo dye, having the formula men
to a violet solution.
tioned at the beginning, is combined with 8
Vegetable ?bers andregenerated cellulose from
neutral or alkaline Glauber salts bath are dyed
vivid red shades which when aftertreated with
cupric salts, become faster to'light and washing.
hydroXy-quinolines. Of the latter B-hydroxy
quinolines itself is primarily suitable, but sub
stituted 8-hydroxy-quinolines such as 5-chlor
B-hydro-xy-quinoline, 8-hydroxy-quinoline-5- and
3 -7—sulphonic acid and 8-hydroxy-quinolin'e-T
Example :12
carboxylic acid may also be used. The coupling
is carried out in an alkaline medium, which may v10
The amino azo dyestuif (obtainable in the
contain, for example, alkali hydroxides such as >
known manner from 20.5 parts of 2-amino-l- '
sodium hydroxide and, if necessary, alkali‘ car
bonates.
The compounds should be chosen so that the
methyl-.ll-phenoxy acetic acid by diazotisation
and coupling with 35.8 parts of 2-(4’-aminoben
?nished dye does not contain more than 2 sul- V
acid in sodium carbonate alkaline medium) , which
phonic acid groups.
The dyes obtained by the present process can
has been “precipitated with sodium chloride,
zoyl) - amino-5-hydroXynaphthalene-'7-sulphonic
filtered and pressed, is suspended in 400 parts of
be used in the usual way for dyeingrand print- ,
water. 'Zparts-of sodium nitrite are added and
the whole is cooled to 6° C. by the addition of
ing the most various animal and, in particular, ‘
cellulosic ?bers such as wool, silk, leather and '20 ice. 30 parts of concentrated hydrochloric acid
are then added and stirred for about 2 hours.
especially cotton, linen,vrayon, and staple ?bers ‘
from regenerated cellulose. Predominantly bluish
The diazocompound obtained is now added to a
red to red to yellowish red shades are obtained.
solution of 14.5 parts of _8-hydr,oxyquinoline, 1.5‘
Particularly valuable products are obtained if
parts of caustic soda and 20 parts of calcined
these dyes are treated in the substance, in the dye 25 soda'in500 parts of water cooled to 4° C. After
bath or on the ?ber with agents which yield
a fewjhours the solution “is warmed to 65° _C. and
metals, principally copper. According to the com
100 110,200 vparts of sodium chlorideare added in
order to obtain an easily ,?lterable {form of the
diazo dyestu? and then the solution vis ?ltered.
and the precipitatedried. A darkbrown powder
position of the dyes, complex metallic compounds,
in particular copper compounds, are obtained,
which are soluble in water and can be used for 30
dyeing according to methods usual for directdye
. of the formula:
ing dyestuffs, or in some cases sparingly soluble 1'
CH3
to insoluble copper compounds which are best pre
pared on the ?ber itself.
. _
Subsequent treatment of the dyestuffs on the
?ber with agents which yield metals (mainly
copper) can be carried out by the usual aftere 7:
treatment with copper in fresh bath or with
advantage in the dye bath ‘itself after dyeing,
is obtained which dissolves in water ‘and dilute
when copper compounds which are stablev to 40 alkalies torred solutions and in concentrated sul
alkalis e. g. complex copper tartrates shouldbe h
used (of. U. S. Patent 2,148,659) .
'
'
'
~- phuricacid to a violetsolution.
Vegetable ?bers anduregenerated cellulose ‘are
dyed vivid yellowish red shades from neutral :or
Example 1
alkaline Glauber’s salt bath which’ when after.
45 treated with vcupric salts become faster to light
The amino azo ,dyestuif (obtainable in the
known manner from 20.3 parts of _2-amino-1- .:;_ andwashing.
inethoxy-benzene-4-su1pho_nic acid ‘by diazotisa
tion and coupling with 35.8 parts of 2-(4'-amino
benzoyl) -.a mi n o-5-hydroxynaphthalene-7 -,s_ul
phonic acid in sodium carbonate alkaline medi
‘Example 3 ‘
a The vaminogazo dyestu?.’ (obtainable in .the
50 known .manner from 13.7 parts .of .2-amino-l
methoxy-A-methylbenzene .by .diazotisation and
um),- which has. been precipitated with sodium
chloride, ?ltered and pressed, is, suspended in v400
parts of ‘Water. 7 parts of vsodium nitrite are
“ added and the Whole is cooled to 6° 7C. ,by the
addition of ice. 30 parts of concentrated ‘hydro
coupling with 35.8 parts of 2- (-4'.-amino-benzoyl).-,
amino-5ehydroxynaphthalene- .7 ;.-sulphonic = acid
in sodium carbonate. alkaline medium) ,7 which
55
chloric acid are addedand stirring. is carried out .
for about 2 hours. " The diazo compound obtained
has been precipitated with sodium chloride, ?l
tered and pressed, is dispersed in AOO-parts .of
water. 7 parts of sodium nitrite are added and
is now added to qa solution of ~,15l.5 parts of'8
the whole is cooled to 6° C. with ice. 30 .parts '
of concentrated hydrochloric acid are then added
and the whole stirred for about2 hours. The di
azo compound obtained is now added to a solution
hydroxy-quinoline, 15 parts of caustic soda and
20 parts calcined soda in 500 parts of water
cooled to 4‘? C. ‘After a few hours the solutionvis
warmed to 65° C. and 100 to 200 parts of sodium
chloride are added in order to obtain an, easily
of 14.5 parts of 8—hydroxyquinoline, :15 parts of
caustic soda and 20 parts of calcined soda in 500
?lterable form ,ofcthediazo dyestu?, and they 65
parts of water cooled to 4° C.
formula:
an easily ?lterableform of the disazo dyestu? and
then the solution is ?ltered andthe precipitate
solution is ?ltered and the precipitate dried. _A
dark brown powder is the result having the
" Hols
90H?’
.
N. ,
NH- o 0» Omar-8.011
After a few hours
the solution is warmed to 65° C. and 1007200 parts
I of sodium chloride are added in order to obtain
dried. The result is a dark brown powder-which
dissolves in water and dilute alkaliestolredsom
tions and in concentrated sulphuric acid to avio
let solution.
7
.
7
-
'
-
Vegetable ?bers and regenerated cellulose‘ are
75 dyed vivid red shades from neutral or alkaline.
2,41 1,646 2
6
Glauber’s salt bath which when after-treated
with cupric salts become faster to light and
Further dystu?‘s obtained according to the
present invention are given in the following
Washing.v
table:
_
Dlazo
components, amino
azo dyestn? from_
Azo component
2-aminobenzoic acid ____________ __
Shade of the
coppeted
dyeing
R-hydroxyquinoline _____ ._v____ _.
H 033
—NH—C 0
Brick red.
——NH;
2‘amino-R-naphthoic acid _______ __
Blluishyred.‘
4-aminobenzoic acid ___________ ._
Dnii red.
2 - amino - 1 - hydroxybenzene - 4 -
Bordeaux.
suifonamide.
.
2-amino-1-phenoxy-acetic acid-4-
Red.
snifonamide.
2-a1nin0-4-chlor-1-phenoxy acetic
ac
Do.
.
2 - amino - 6 - chior - 1 - hydroxy -
Bordeaux.
bcnzene-4-sulionic acid.
2 - amino -1 - hydroxybenzene - 4 —
suifonic acid.
,
D0.
Monosulfonated 2-amino-4-ch1or-
Red.
l-methoxybenzene.
I
2-aminobenz0ie acid ____________ ._
.
.‘Z-amino-i -methoxy-4-mcthylbenzenc.
_
5-chlor-S-hydroxygu1nol1ne ____ __
Yeilowish red.
8 - hyéiroxyquinoline - sulphonic
Red.
aci
.
Do ______________________________ __do _____________________________________________ __ 8-hygiiroxyquinoline-7-carboxylic
aci
D0.
.
2-amino~4-chior-l-phcnoxy-acetic _____do ____________________________________________ __ 8- hygroxyquinoline - 7 - sulfonic
acid.
'
Zaminobenzoic acid_'. __________ __
aci
Yellowish red.
.
8-hydroxyqnin01ine ___________ ._
H 0 3S
Do.
"
’
—NH—C O
OH
2-an1ino-3-naphthnic acid _______ __ _
-_do__
_._-_do ........................ ..
2-arnino-4-chlor-l-phcnoxy-acctic _____do _________________________________________________ _.d0 ________________________ ._
aci
Bordeaux.
Yellowish red.
'
Z-amino-l-mcthoxy-4-methy1- _____do _________________________________________________ _.do ________________________ __
Do.
benzene.
2~amino -1-hydroxybcnzcnc-4- _____do _________________________________________________ ._d0 ____________________ _.-..__
Bordeaux.
suifonamide.
.
4-aminobenzoic acid _________________ __do _________________________________________________ __do ____________ _T_-___ ______ ..
Z-aminobcnzoic acid ___________ _.
._do._
Reddish orange,
5-ch.lor-8-hydroxyqu1nohne_._;_.
2 - amino -1 - hydroxybenzene ~ 4 -
.-___do ________________________ ._
suliouamide.
_
2-amino-l-methoxy-4-m ethylben-
v
zenc.
acid.
'
-
Bordeaux.
‘ H 1
E-hydroxyquinoline .......... .;-
ionic acid.
Binish red.
_
8 - hydroxyqumohnc - 7 - suifonlc
2-an1ino-1-methoxybenzene~4-snl-
Do.
2-amin0-1~methoxy-4-methy1bcn-
I 'Do.
Do.
zene.
H 0.25
i
—
i
O H ,
.
2 aminobenzoic acid . . _ _ _ . _ _ _ _ _ _ _ _
v
v
. _ _ “do ________________________ _.
N=C~
'
H OzS-l
l
—NE
.
~
~
.
Yeiiowish red.
.
l
NH: .
=
u
2-amino-1-phenoxy-acetic acid____
Brownish red. _‘
2 - amino - 4 - chlor - 1 - hydroxy-
Bordeaux.
benzene-Fi-sulfonic acid.
4-aminobenz0ic acid ____________ -_
4 - amino - 1 - hydroxybenzene - 2 -
~carboxylic acid.
a
Red,
‘Bijoymt
,
.
_
.l
‘ ‘ H >
_
7
Dlazo-component's, amino-azo-dyestu?-irome"
Azo-compon'ent
2-amino-3-naphthoic acid _______ __
coglgzgggfiggggl
8-hydr0xyquinoline ____________ __ ' Bordeaux.
'
H028
‘
IV
I
—NE
NH:
H
2-a1nino-4-chlor-l-phenoxy-acetic
ac:
.
Bluish red.
_
_
2-amino-l-methoxybenzene-li-sulfonic acid;
’
~
g
Sulionated 2-amino-l-methoxy-4~
,
‘ Red.
methylbenzene.
'
Sulionated 2~amino-l-methylben~
zene.
_
f Yellowishred;
~
_.
I
'
- Yellowlsh red.
'
2-amino-l-benzoic acid. -_. ..... ._
5-chlor-8-hydroxyquinoline;-_,-._
6 -nitro ~2-amino - 1 -hydroxyben-
.. .--d0 ........................ _.
zeneA-sulfonic acid.
4-nitro-2-amino-l-hydroxyben-
Do.
..___do ........................ _.
zene-B-sullonic acid.
_
2-amino-l-mlethoxyA-methylben-
_
,
S - hYéll‘OXYqlllDOllDG - 7 - suliomc
zene.
aci
I
Bordeaux.
Do;
~
Do;v
..
ing carried out during half-an-hour at '70-80” C.
Example 4
The cotton is now thoroughly rinsed and if neces
The diazo compound from 13.7 parts of 2»
aminobenzoic acid is coupled at room temperaj
ture in the presence of an excess of sodium car
bonate with 37.2 parts of 4’-aminophenyl-5-‘
hydroxy- 7 -sulpho-lzz-naphtho-thiazole. After
30
sary soaped and ?nishedoff as usual.
It‘ is dyed
red and is fast to‘ light and washing.
What I claim is:
'
‘
>
1. A process for the manufacture of a disazo
dyestu?, which comprises coupling, with an 8
hydroxyquinolin‘e capable of coupling, a diazo
tized aniinoazo compound of the formula
a few hours the coupled mixture is warmed and
the monoazo dyestu? is precipitated by the addi-‘
tion of sodium chloride and ?ltered. This dye
stu? is dissolved in 1000 parts of water- anddiazo
tised at 4° C. by adding '7 parts of sodium nitrite
and 35 parts of concentrated hydrochloric acid.‘
After the diazotisation is’ complete, the suspen
sion of the diazoazo compound is neutralized with
soda and the solution containing 14.5 parts of 8 40 wherein X stands for a link including the are
rangement
hydroxyquinoline in 200 parts of 10% caustic
sodasolution is added. A red disazo dyestuff is
0H
.
-
Y\ 0;.
formed of the formula:
/
—N
V
s-c-
‘Hogs-l
N=N-
’
wherein Y is a member selected from the group
consisting of oxygen and a member of a' hetero
N1
NzN’
coon on
OH
r
..
cyclic ring leading to the 1-position of the naph
. thalene nucleus, and wherein Rrstands for an
50 aryl radical.
2. A process for the manufacture of a disazo
dyestuiT, which comprises coupling, with an 8-hy
1
droxyquinoline capable of coupling, 9," diazotize'd‘
which is precipitated after a time by’ warming
aminoazo compound of the formula
and addition of sodium chloride. After ?ltering 55
and drying a dark powder is obtained which dis-‘
solves in water and dilute alkalies to red solu
tions. _It dyes vegetable ?bers as well as arti?-»
cial '?bers from regenerated cellulose bluish red
shades which when after-treated with a cupric 60
salt solution become fast to light and washing.
Example 5
wherein X stands for a. link selected from’ the
- class consisting of
100 parts of. cotton are entered at 40° C. into a 65
dyebath of 3000 parts of water which contains 1
part of the dyestuff obtained accordingto Exam
pie 1 as well as 2 parts of sodium carbonate, and
the temperature is raised to 90 to 95° C. 30 parts ‘
of crystallised sodium'sulphate are added and 70
dyeing is continued for three quarters of an hour
at 90» to 95° C; The'dyebath is then cooled to
wherein the carbon atomv is in? each ‘case. cone"
70° C., the necessary quantity of a'solution ore
complex copper tartrate rendered weakly; alka
linewith sodium carbonate is added‘ and copper‘
nected to the phenylenev group, thebonddesig- '
jnate'd'by (‘1) is‘ connectejd'to the: li-positiori of‘
~
the naphthalene nucleus and the bond desig~v '
2,411,646
9
10
nated by (2) being linked to the 2-position of
the naphthalene nucleus, and wherein R1 stands
where X stands for a, link selected from the class
‘
consisting of
'
'
for an aryl radical containing at least one sub
stituent capable of promoting the formation of
complex metal compounds.
3. Process for the manufacture of a disazo
dyestuff, which comprises coupling a diazotized
aminoazo compound of the formula
10
NH?
wherein the carbon atom is in each case con
nected to the phenylene group, the bond desig
nated by (l) is connected to the 1-position of
OH
wherein R1 stands for an aryl radical containing 15 the naphthalene nucleus and the bond designated
at least one substituent capable of promoting the
by (2) being linked to the 2-position 0f the
formation of complex metal compounds, with an
naphthalene nucleus, R1 stands for an aryl' radi
g-hydroxyquinoline capable of coupling.
cal, and R3 stands for the radical of an 8-hydroxy
4. Process for the manufacture of a disazo
quinoline coupling component.
dyestu?", which comprises coupling a diazotized 20
8. Process for the manufacture of a disazo
aminoazo compound of the formula
dyestuff comprising coupling the diazotized ami
il=f®
HOaS
noazo compound of the formula
NHg
25
AH
wherein R1 stands for an aryl radical containing
at least one substituent capable of promoting the
formation of complex metal compounds, with an
$0311
8-hydroxyquinoline capable of coupling.
with 8-hydroxy-quinoline.
5. Process for the manufacture of a dis-azo
9. Process for the manufacture of a disazo
dyestuff, which comprises coupling a diazotized
aminoazo compound of the formula
H
dyestuff comprising coupling the diazotized ami
noazo compound of the formula
.
wherein R1 stands for an aryl radical containing
atleast one substituent capable of promoting the
formation of complex metal compounds, with an
COOH
OH
with S-hydroxy-quinoline.
8-hydroxyquinoline capable of coupling.
Y
_
10. Process for the manufacture of a disazo
6. A disazo-dyestuff of the formula
dyestuff comprising coupling the diazotized ami
noazo compound of the formula
eC-Q-m
I]
wherein X stands for a link including the ar
arrangement
Y
—N
|
$11
COOH
\
C_
/
with 8-hydroXy-quino1ine.
'
11. Disazo-dyestuffs of the general formul
wherein Y is a member selected from the group
consisting of oxygen and a member of a hetero
cyclic ring leading to the 1-position of the naph
thalene nucleus, R1 stands for an aryl radical,
and R3 stands for the radical of an 8-hydroxy
quinoline coupling component.
'7. A clisazo-dyestuff of the formula
70
H
wherein X stands for a link containing at least
one nitrogen and at least one carbon atom di
rectly attached to each other, connecting at least
OH
75 one of the positions 1 and 2 of the naphthalene
' ‘$2,411,646
11
vnucleus With'the phenylene radical, the "nitrogen
12
14. A disazo-dyestuff of‘the formula '
being connected to the naphthalene nucleus ~and
the carbon atom to the phenylene radical, where
in R1 stands for an aryl radical, and R3 stands for
the radical of a 84hydroxy-quinoline coupling
component.
12. Disazo-dyestuffs of the general formula
wherein R1 stands ‘for an aryl radical containing
at least one substituent capable of promoting the
formation of complex metal compounds, and R3
stands for a 8-hydroxy-quinoline radical.
15. A disazo-dyestuff of_ the formula
. H-Q
wherein X stands for a link containing at least
one nitrogen and carbon atom directly attached
to each other, connecting at least-one of .the .posi
tions 1 and 2 of the naphthalene nucleus With
the phenylene radical, the nitrogen being con
nected to the naphthalene nucleus and the car
bon atom to the phenylene radical, wherein R1
HOaS——
stands for an aryl radical containing at least one
substituent capable of promoting the formation ‘
of complex metal compounds, and R3 stands for
the radical of a 8-hydroxy-quinoline coupling
wherein R1 stands for an aryl radical containing
at least one substituent capable of promoting the
formation of complex metal compounds, and R3
stands for a 8-hydroXy-quinoline radical.
16. The disazo-dyestuff-of the formula
component.
17. The .disazo-dyestu? of the formula
on
18. The disazo-dyestuff of the formula
13. A disazo-dyestuff ‘of the formula
Hols-4
50
‘H O as
N
_N=N_
OOH
wherein R1 stands for an aryl radical containing 55
at least one substituent capable of promoting the
formation of complex metal compounds, and R3
stands for a 8-hydroxy-‘quinoline radical.
H
v
WALTER ANDERAU.
‘
Certi?cate ‘ of Correction
Patent No. 2,411,646.
November 26, 1946.
WALTER ANDERAU
It is hereby certi?ed that errors appear in the printed speci?cation of the above
numbered patent requiring correction as follows: Column 4, line 29, Example 2, for
the Word “diazo” read disazo; column 9, line 38, claim 5, for that portion of the
formula reading “S__C——” read S
(J——; and that the said Letters Patent should
be read With these corrections therein that the same may conform to the record of
the case in the Patent O?ice.
'
Signed and sealed this 25th day of February, A. D. 1947.
LESLIE FRAZER,
First Assistant Commissioner of Patents.
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