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Патент USA US2117569

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2,117,569
Patented May 17, 1938
UNITED STATES PATENT OFFECE
2,117,569
DYESTUFFS OF THE ANTHRAQUINONE SE
RHES AND A. PROCESS FOR THEIR MANU
FACTURE
ltibin Peter, Basel, Switzerland, assignor to the
?rm Chemicalworks formerly Sandoz, Basel,
Switzerland
No Drawing. Application June 8, 1937, Serial
Ne. 147,145. In Switzerland June 18, 1936
10 Claims. (Cl. 260-430)
sulphonated anthraquinone compounds at a tem
The present invention relates to new anthra
quinone dyestuffs and to a process for their man
ufaoture.
It has been found that new anthraquinone dye
perature of 90-15%" C., preferably under stirring
and in presence of an alkaline compound in suf
?cient quantity to neutralize the sulphurous acid
split off during the reaction. In order to facili
giving brilliant shades on animal ?bres can be tate the reaction and to obtain pure products
prepared, if anthraquinone compounds or" the‘ it is often advantageous to carry out the reaction
under addition of an organic solvent, such as ni
general formula
5 stuffs possessing excellent iastness to light and
trobenzene, nitronaphthalene, pyridine, quinoline
or of mixtures thereof. The condensation prod 10
ucts thus obtained can be isolated from the re
action mixture in the usual manner by diluting
1O
15
20
wherein B represents hydrogen or a sulphonic
acid group, X represents an alkyl group, Y repre
sents a halogen or an alkyl group, Z represents
hydrogen and alkyl and V stands for hydrogen
or a sulphonic acid group, are heated with di
or trivalent alcohols or their ethers containing
at least one free aliphatic hydroxy group in pres
ence of strong basic compounds and if the prod
25
ucts thus obtained are eventually subjected to a
treatment with sulphuriciacid in order to sul
phonate them or to transform them into sulphuric
acid esters. On heating the above cited com
30
pounds with the polyvalent alcohols, the‘sulphonic
acid group in Z-pcsition will be replaced by a hy
droxyalkyl or an esteri?ed hydroxyalkyl group.
On treatment with sulphuric acid, dyestuffs will
be obtained which contain a sulphonic acid group
in the aryl radical or in the case that there is a
free hydroxy group in the hydroxyalkyl radical,
they will be esteri?ed in this group.
As alcohols which can be used for the manu
facture of the new dyestuffs, ethylene glycol, the
polyglycols, glycerol and the like and also their
4O
ethers containing at least one free aliphatic hy
droxy group, such as ethyleneglycolmono~methyl
or -ethyl- or -buty1ether, polyethyleneglycol
monomethyl- or -ethyl- or -butylether, oc-XYIBIlYl
glycerineether etc., can be cited.
As strong alkaline compounds there may be
employed the alcoholates, hydroxides and car
bonates of alkali metals.
i
The replacement of the sulphonic acid group
50 in 2-position can be performed by heating the
with water or with ethanol, whereby the base be
comes precipitated.
If the base thus obtained is insoluble in water,
it is subjected after drying to a treatment with 15
sulphuric acid. In cases where the base contains
a free hydroxy group in the alcoholic radical, it
is esteri?ed by simple dissolving in concentrated
sulphuric acid, or in monohydrate, at a tempera
ture of 0-30° C. If it is intended to introduce 20
a sulphonic acid group into the aryl radical, the
base is treated with weak monohydate at a tem—
perature of 30-60° C.
If the starting compounds contain besides the
sulphonic acid group in Z-position another sul
phonic acid group in the molecule, the reaction
products obtained by the present process will be
soluble in water without treatment with sulphuric
acid, but in order to increase their solubility they
can naturally be subjected to sulphonation or to 30
esteri?cation with sulphuric acid. The sulphon
ated compounds thus obtained are isolated from
the reaction mixture in the usual manner, for
example by mixing them with water or ice-salt
water, whereby they become precipitated and can 35
be ?ltered oii.
One object of the present invention is the
process for manufacturing new dyestuffs of the
anthraquinone series, consisting in heating an
thraquinone compounds of the general formula
NEg
2
2,117,569
wherein B stands for hydrogen or a sulphonic
and dyes wool and natural silk in a brilliant pure
acid group, X stands for alkyl, Y stands for halo
gen or alkyl, Z stands for hydrogen or alkyl and
violet possessing very good fastness to light.
V stands for hydrogen or a sulphonic acid group,
with di- or trivalent alcohols or their ethers, con
dyestuff of the formula
If instead of glycol one uses glycerol, a similar
taining at least one free aliphatic hydroxy group,
in presence of strong alkaline compounds and
eventually subjecting the compounds thus ob
tained‘ to a treatment with sulphuric acid.
10
Another object of the present invention is the
10
water-soluble anthraquinone dyestu?s of the gen
eral formula:
CH3
(EH:
15
—A
will be obtained.
The potassium hydroxide used for the conden
sation can also be replaced by potassium car
bonate or sodium carbonate.
Example 2
wherein A represents an oxalkyl or a sulphonated
oxalkyl group, B stands for hydrogen or a sul
20
10 parts of sodium hydroxide or potassium hy
droxide are dissolved in 100 parts of glycerol and
10 parts of the dyestuff of the formula
25 phonic acid group, X stands for alkyl, Y stands
for halogen or alkyl, Z stands for hydrogen and
alkyl and V stands for hydrogen and a sulphonic
30
acid group, which dyestuffs dye animal ?bres in
brilliant red to violet shades of good fastness to
light.
The following examples, without being limita
tive, illustrate the present invention, the parts
being by weight:
Example 1
20 parts of the dyestuff of the formula
NH:
40
/
00
are added thereto. After stirring for one hour at
120° C. the reaction mixture is allowed to cool
down, diluted with alcohol and the precipitated
base ?ltered. The condensation product thus ob
tained is isolated as described in Example 1 and
esteri?ed with sulphuric acid.
\
—SOaN-a
This dyestuff pos
sesses the formula
V45
are introduced into a hot solution of 10 parts of
50
potassium hydroxide in 100 parts of ethylene gly
col and heated under stirring during 2 hours at
100~110° C.
50
When a test taken therefrom shows
that the product became completely insoluble in
water, the reaction mixture is diluted at 80° C.
with 100 parts of ethanol or of water, allowed to
cool down and the precipitated base is ?ltered,
Washed and dried. The base thus obtained is
then dissolved in ?ve times its weight of concen
trated sulphuric acid at 15° C. After short stir
60 ring, a test shows that the base became water
soluble.
|
CH3
The reaction mass is then poured on an
ice-salt water mixture, the dyestul‘f ?ltered, di
luted with water, neutralized and salted out by
means of sodium chloride. The dyestuif isolated
65 in this manner possesses the formula
and dyes wool and silk in a brilliant red violet
shade.
Example 3
20 parts of potassium hydroxide are dissolved
in 500 parts of warm ethylene-glycclmonoethyl
ether and into the solution thus obtained are in
troduced 50 parts of the dyestuff used in Example
1. The reaction mass is then stirred at 100-105°
C. until a test taken therefrom became no more
redder in alcohol.
The reaction mass is then
diluted with ethanol, cooled down and the base
which crystallizes out, is isolated in the usual
manner.
00
/
\
00/
OCHr-CH:—OSO:H
I
on
|
3
10 parts of this base are dissolved in 50 parts
of sulphuric acid monohydrate and treated below
30° C. with 15 parts of weak oleum. After stir
ring for a short time at 30° C., a test shows that
the base becomes water-soluble. The dyestu? is
precipitated by pouring the sulphonation mix
75
|
ture on ice-salt water mixture, ?ltered and neu
tralized.
75
3
2,117,569
The dyestuif thus obtained possesses the for
mula
heating anthraquinone compounds of the general
formula
'
N132
NH:
/
CO
o0
\
oom-om-oclm
\
soan
B___
X
OHa
NH
I
NH
OH:
10
|
CHa
V
5 ;——Z
10
S 03H
Y
and dyes wool in brilliant red-violet shades of
good fastness to light, to washing and to perspi
ration.
Similar deystu?s are obtained, if the compound
of the formula
wherein B represents one of the group consisting
of hydrogen and a sulphonic acid group, X rep
resents one of the group consisting of methyl and
ethyl, Y represents one of the group consisting 15
of halogen, methyl and ethyl, Z represents one
of the group consisting of hydrogen, methyl and
ethyl and V represents one of the group consist
ing of hydrogen and a sulphonic acid group, with
an alcohol selected from the class consisting of 20
di- and trivalent aliphatic alcohols‘ and their
ethers containing at least one free aliphatic hy
20
SOaNa
droxy group, in presence of a basic compound se
lected from the class consisting of alcoholates,
|
C2115
is condensed with the above cited glycol ether or
with a diethyleneglycolmonoalkyl ether or with
an arylglycerineether.
hydroxides and carbonates of alkali metals at a 25
temperature of 90-150° C.
2. A process for the manufacture of water-sol
uble anthraquinone dyestu?s, comprising heating
anthraquinone compounds of the general for
30
30
Example 4
Into a solution of 10 parts of potassium hydrox
ide in 100 parts of glycol are introduced 10 parts
5 of the dyestuff obtained by condensing a mixture
35
consisting of l-amino-4-bromo-anthraquinone
2,5- and 2,8-disulphonic acids with l-amino
2,4,6-trimethylbe‘nzene and stirred during one
hour at 120° C. After cooling down, the reaction
4 O mass is diluted with water and the precipitated
dyestuff ?ltered off. It dyes wool in a bluish
violet shade, which on esteri?cation with sul
phuric acid, gives a redder and more easily sol
uble dyestuff.
-
Example 5
wherein B represents one of the group consisting 40
of hydrogen and a sulphonic acid group, X repre
sents one of the group consisting of methyl and
ethyl, Y represents one of the group consisting
of halogen, methyl and ethyl, Z represents one
of the group consisting of hydrogen, methyl and 45
ethyl and V represents one of the group consisting
10 parts of potassium hydroxide are dissolved
in 100 parts of warm glycerine. To this solution
are added 10 parts of the potassium salt of 1
amino - 4 - (2’,4'-dirnethyl-6'-bromo) phenylami
noanthraquinone-2~sulphonic acid, 10 parts of
pyridine and 2 parts of ntrobenzene and the re
action mixture is stirred at 110° C., until a test
is no more soluble With a blue coloration in water.
The reaction mass is then diluted with hot water,
the precipitated base ?ltered o?, Washed and
dried. The dry base is then esteri?ed with sul
phuric acid monohydrate and the dyestuff iso
lated as described in Example 1. It possesses the
(ill formula
of hydrogen and a sulphonic acid group, with an
alcohol selected from the class consisting of di
and trivalent aliphatic alcohols and their ethers
containing at least one free aliphatic hydroxy
group, in presence of a basic compound selected
from the class consisting of alcoholates,hydroxides
and carbonates of alkali metals at a temperature
of 90-150° C. and of an organic solvent selected
from the group consisting of mononitrobenzene, 55
mononitronaphthalene, pyridine and quinoline.
3. A process for the manufacture of water-sol
uble anthraquinone dyestuffs, comprising heating
an anthraquinone compound of the general for
mula
/
oo
IIQ’HQ
\
NH:
.
OO
o om-onon-om-msom
—S OaH
B__ __
\C O /
C H:
l
NH
|
Z
Y
and dyes wool in a reddish, brilliant violet shade
of good fastness to light.
I claim:
1. A process for the manufacture of water
anthraquinone
65
v
I
Br
75 soluble
X
\/\CO/
dyestuffs,
comprising
70
wherein B represents one of the group consisting
of hydrogen and a sulphonic acid group, X rep
resents one of the group consisting of methyl and
ethyl, Y represents one of the group consisting
of halogen, methyl and ethyl, Z represents one 75
4
2,117,569
of the group consisting of hydrogen, methyl and
ethyl and V represents one of the group consisting
of hydrogen and a sulphonic acid group, with an
alcohol selected from the‘class consisting of di
and trivalent aliphatic alcohols and their ethers
containing at least one free aliphatic hydroxy
group, in presence of a basic compound selected
from the class consisting of alcoholates, hydrox
with glycerol in presence of potassium hydroxide
and of pyridine and nitrobenzene at 110° C.
and subjecting the condensation product thus ob
tained to a treatment with concentrated sul
phuric acid at 15° C. in order to transform it
into the sulphuric acid ester.
7. The water-soluble anthraquinone dyestuffs
of the general formula
ides and carbonates of alkali metals at a tem
NHz
10 perature of 90-150° C. and of an organic solvent
10
selected from the group consisting of mononitro
benzene, mononitronaphthalene and quinoline,
andsubjecting the condensation product thus ob
tained to a treatment with concentrated sul
phuric acid at av temperature of 0-30° C.
4. ‘A process for the manufacture of a water
soluble anthraquinone dyestuff, comprising heat
ing the anthraquinone compound of the formula
wherein A represents one of the group consisting
of an hydroxyalkyl and a sulphonated hydroxy
alkyl group, B represents one of the group con 20
sisting of hydrogen and a sulphonic acid group,
X represents one of the group consisting of methyl
and ethyl, Y represents one of the group consist
ing of halogen, methyl and ethyl, Z represents
25
one of the group consisting of hydrogen, methyl
and ethyl and V represents one of the group con
CH3
with ethyleneglycol in presence of potassium hy
droxide at IOU-110° C. and subjecting the con
densation product thus obtained to a treatment
with concentrated sulphuric acid at 15° C. in order
to transform it into the sulphuric acid ester.
5. A process for the manufacture of a water
35
NH:
0/ \O—OCH2—,CHa—OSOsH
NH-O-CHa
soluble anthraquinone dyestuff, comprising heat
\C 0/
IYTH,
O: \O_SO3H
00/
on
I
|
3
with glycerol in presence of potassium hydroxide
at IOU-110° C. and subjecting the condensation
product thus obtained to a treatment with con
centrated sulphuric acid at 15° C. in order to
50 transform it into the sulphuric acid ester.
6. A process for the manufacture of a water
soluble anthraquinone dyestuff, comprising heat
ing the anthraquinone compound of the formula
55
—SOaH
co
3
40
IITH:
0/ :O~0cm—o130H-om—oson1
NH—®-cm
CH
'
\oo
I
|
a
CllHa
50
10. The anthraquinone dyestu? of the formula
NHz
/O°\ l
GOO/O Q-m
Rag
60
1
éHs
|
NH:
on
I
9. The anthraquinone dyestu?" of the formula
OH:
45
I
00
ing the anthraquinone compound of the formula
00
40
sisting of hydrogen and a sulphonic acid group,
which dyestuffs dye animal ?bres in brilliant red
to violet shades of good fastness to light.
8. The anthraquinone dyestuff of the formula 30
OCHz-C
5-5
(IJHa
|
Br
ALBIN PETER.
60
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