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Патент USA US2108126

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2,108,120
Patented Feb. 15, 1938
UNITED STATES PATENT OFFICE
2,108,126
AZO-DYESTUFFS OF THE ANTHRAQUINONE
SERIES
'
Ernst Honold, Frankfort-on-the-Main-Fechen
heim, and Carl Taube, Wiesdorf, near Cologne
on-the-Rhine, Germany, assignors to General
Aniline Works, Inc., New York, .N. Y., a cor
poration of Delaware
No Drawing. Application October 21, 1936, Se
rial No‘. 106,830. In Germany October 23,
1935
4 Claims. (Cl. 260—56.5)
The‘ following examples illustrate, but do not
This invention relates to valuable new 'azo
dyestuffs, more particularly to those of the general limit the invention, the parts being by weight.
formula:
Example 1
Y
I
45 parts of the sodium salt of 1-amino-4
—S OaNa
bromo—anthraquinone-Z-sulfonic acid and 35
wherein X stands for a member selected from the
group consisting of hydrogen and acylamino, Y
15
stands for a member selected from the group con
sisting of -—NH2 and -—OI,-I, R1 stands for a
radicle selected from the group consisting of the
benzene and phenyl-pyrazolone series, R2 means
aradicle of the benzene series‘ and R1‘ and R2
contain at least one member selected from the
group consisting of hydrogen, -SO3Na and
—COONa.
The new dyestu?s are obtained by condensing
parts of the sodium salt of 4—amino—azobenzene
4'-sulfonic acid are dissolved in about 2000 parts
of water, 20 parts of sodium bicarbonate and 1 10
part of cuprous chloride are added and the mix
ture is heated to about 801-90° C. for about 10
hours while stirring. Then the solution is ?ltered
while hot and the condensation product formed is
isolated from the ?ltrate by the addition of 15
sodium chloride. It is dissolved in hot water in
order to remove unaltered initial materials, the
dyestu? is precipitated by the addition of con
centrated hydrochloric acid, ?ltered off and
washed with dilute hydrochloric acid. Then the 20
dyestuif is dissolved once more in water with
addition of sodium carbonate, precipitated from
this solution by the addition of sodium chloride,
l-amino - ¢l_- halogeno — anthraquinone - 2 - sulfonic
?ltered off and‘ dried.
acids or l-‘hydroxy-llehalogenoanthraquinone-2e
sulfonic acids or the substituted derivatives
thereof with aminoazo compounds of the general‘
formula:
It is a greenish black
powder, soluble in concentrated sulfuric acid with 25
a violet color, dyeing wool from an acid bath
very fast olive-green shades. The new dyestu?
corresponds to the formula:
(I?
wherein R1 and R2 have they above signi?cance.
Particularly useful are aminoazo compounds‘ of
NH;
30
SOaNa
this general formula which contain one or more
groups inducing solubility in water such as for
35 example the carboxyl group or the sufonic‘v acid
group.
‘
Advantageously the condensation is performed
\d/ ILIH—<:>—N= Q-SOaNa
35
Example 2
in an aqueous medium or, when employing com
pounds which are only slightly soluble in water,
40 in a mixture of water and alcohol. It is surpris
ing that the said aminoazo compounds can be
condensed with l-amino- or l-hydroxy-li-halo
geno-anthraquinone-2-sulfonic acids, in spite of
the fact that they contain the negative azo group
and, possibly, a further strongly negative group
such as the sulfonic acid group.
'
The new dyestuffs thus obtained possess a par
ticularly-great a?inity for animal ?bers which are
dyed from an acid. bath‘ olive-green to’ green
5 O shades of excellent fastness.
Moreover the new
products possess an affinity for cotton which is
quite considerable in some cases, and some of
them are valuable intermediates for the manu
.55
iacture of other dyestu?s.
45 parts of the sodium" salt of l-amino-ll 40
bromo-anthraquinone-2-sulfonic acid are dis
solved in about 1000 parts of water. ‘20 parts of
sodium bicarbonate, 1 part of cuprous chloride
and the solution of 25 parts of ‘l-amino-azo
benzene in about 800 parts of alcohol are added 4.5
and the mixture is heated to boiling for about 12
hours in‘ an“ apparatusprovided with'a re?ux con
denser and a stirrer. Then the alcohol is distilled
off, the solution is ?ltered and from the ?ltrate
the condensation product formed is isolated by _
the addition of sodium chloride. It is dissolved
in water, precipitated by the addition of hydro
chloric acid while hot and the precipitate is
?ltered off and washed with dilute hydrochloric
50
2
2,108,126
acid. Then the condensation product obtained of
the formula:
‘i re
water with an olive-green color. “It dyes ‘Wool
fast olive-green shades.
Example 5
50 parts of the sodium salt of 1-amino-4-bro
mo-5-methoxy - acetylamino - anthraquinone - 2
sulfonic acid and 30 parts of the sodium salt of
4-amino-2-methyl-azobenzene-4'-carboxylic acid
l
is dissolved in alcohol and precipitated by the
addition of cold water.
When dry it is a green
ish black powder, soluble in concentrated sul
furic acid with an olive color and in sulfuric acid
15 of 85 per cent H2804 with a reddish violet color.
Example 3
45 parts of the sodium salt of 1-amino-4-bro
mo-anthraquinone-2-sulfonic acid are condensed
20 with 35 parts of the sodium salt of 4-amino-2
are dissolved in about 1000 parts of water, 20 parts
of sodium bicarbonate and 0.5 part of cuprous 10
chloride are added and the mixture is heated to
about 90 to 100° C. for some hours while stirring.
Then the solution is ?ltered and from the ?ltrate
the condensation product formed is isolated by
the addition of sodium chloride. It is puri?ed
by dissolving in water and precipitating by means
of hydrochloric acid. Then it is dissolved in Wa
ter again with addition of sodium carbonate and
the sodium salt of the new dyestuif of the for
mula:
20
0
NH:
CHI
25
|
|
H30 0 OHBC ONE 0
methyl-azobenzene-‘l'-sulfonic acid in the same
The dyestu?
obtained of the formula:
30 manner as described in Example 1.
0
NH;
is isolated by the addition of soduim chloride. It
is when dry a greenish black powder, soluble in 30
concentrated sulfuric acid with a red (dichro
iczblue) color and in water with an olive-green
color, dyeing wool fast olive-green shades.
Similar dyestuffs are obtained by starting from
SOsNa
l-amino-Ll-bromo-anthraquinone-2-sulfonic acids
35
which contain other acylamino-groups in the 5
position of the anthraquinone nucleus.
By employing 45 parts of the sodium salt of 1
amino-4-bromo—anthraquinone-2-sulfonic
acid
40 may also be puri?ed as described in Example 1.
instead of the sodium salt of 1-amino-4-bromo
It is when dry a greenish black powder, soluble
in concentrated sulfuric acid with a red color,
dyeing wool more yellowish olive-green shades of
5—methoxyacetylamino-anthraquinone-2 - sulfon
good fastness properties.
45
E mample 4
same manner as described in Example 1.
The
condensation product obtained of the formula:
0
55
NH;
45 parts of the sodium salt of l-amino-li-bro
mo-anthraquinone-2-sulfonic acid and the am
S O aNa
50
inoazo dyestu? which is obtained by combining
the diazo compound of 40 parts of l-aminoben
zene-ZA-disulfonic acid with the corresponding
clone in an aqueous solution containing an ex
(I) C H;
55
cess of sodium carbonate are dissolved in about
2200 parts of water. '75 parts of sodium car
bonate and 1 part of cuprous chloridev are added
and the mixture is heated to boiling for about 3 60
60
OH:
is easily puri?ed by dissolving in water and pre
cipitating by means of hydrochloric acid. The
65
It is when dry a
greenish black powder, soluble in concentrated
45
sulfuric acid with a red (dichroic:blue) color,
dyeing wool fast olive-green shades.
Example 6
amount of 1-(3’-aminophenyl) -3-methyl-pyraz—
S OaNa
40
ic-acid in the above example a similar dyestu?’
is obtained which may be puri?ed in the same
manner as above described.
45 parts of the sodium salt of l-amino-ll-bro
mo-anthraquinone-2-sulfonic acid and 40 parts of
the sodium salt of ‘l-amino-3-methoxy-6-methyl
50 azobenzene-2'-sulfonic acid are condensed in the
35
soduim salt of the new dyestuff represents when
dry a greenish black powder, soluble in concen
trated sulfuric acid with a bluish color and in
hours in an apparatus provided with a re?ux con
denser and a stirrer. Acetic acid is added when
cool, and the precipitate formed is ?ltered off, dis
solved in a dilute solution of sodium carbonate
and precipitated therefrom by the addition of
sodium chloride. The dyestuif thus obtained of 65
the formula:
0
NH:
70
70
75
75
3
12,108,126
is when dry a dark powder, dyeing wool fast
bluish green shades.
*
Example 7
45 parts of’ the sodium salt of 1-am1no-4
bromo-anthraquinone-2-sulfonic acid are con
densed with 35 parts of 4-aminoazobenzene-4'
carboxylic acid in an aqueous solution in the
presence of 25 parts of sodium carbonate and 2
10 parts of cuprous chloride by heating to about 90
to 100° C. for some hours. The dyestuif formed
of the formula:
0
NHa
ll
1
15
and is a greenish black-powder, soluble in con
centrated sulfuric acid with a blue color which
is changed to olive-green by the addition of para
formaldehyde. The dyestuff dyes wool froman
acid bath very fast grayish olive shades turning
chromium complex compound.
By employing 2-methyl-4-amino-5-methoxy
benzene-azo-ll’-ethoxybenzene-2’-sulfonic acid 10
instead of the 4-amino-azobenzene-4’-su1fonic
acid in the above example a dyestu? is obtained
which dyes wool very fast olive shades. When
the dyestuff is converted into its chromium com
plex compound olive shades of good fasteness to 15
fulling and potting are obtained.
By condensing
quinone-Z-sulfonic
II
I
20
is isolated and puri?ed as described in Example 1.
It is when dry a greenish black powder, soluble
in concentrated sulfuric acid with a violet color
which is changed to olive-green by the addition
25 of paraformaldehyde. The new dyestuff dyes wool
from an acid bath very fast green shades.
Example 8
By employing instead of the 4-amino-azoben
of
1-hydroxy-4-bromo-anthra
acid with 3-methoxy-4
amino-azobenzene-3'-sulfonic acid a dyestuff is
obtained which dissolves in concentrated sulfuric
acid with a blue color turning to olive-green by
the addition of paraformaldehyde. The dyestuff
dyes wool from an acid bath yellowish olive
shades turning to more yellowish olive of excel
lent fastness properties when converting the dye
stu? into its chromium complex compound.
We claim:
1. The monoazo dyestuffs of the general for
mula:
0
30
Y
I
30 zene-4'-carboxylic acid in Example 7 the same
amount
5
to olive-green of good fastness to fulling and
potting when converting the dyestuff into its
4-amino-azobenzene-3'-carboxylic
——SOaN3.
acid and proceeding as described in Example 7
a dyestuif of the formula:
0
1
35
Y N
NH:
I
—SO3NB
wherein X stands for a member selected from the
group consisting of hydrogen and acylamino/Y
COONa
40
is obtained, which is when dry a greenish black
powder. It disolves in concentrated sulfuric
acid with a reddish violet color which is changed
to green by the addition of paraformaldehyde.
The new dyestuff dyes wool from an acid bath
very fast green shades.
Example 9
50
38 parts of the copper salt of l-hydroxy-ll
stands for a member selected from the group con
sisting of —-NH2 and —OH, R1 stands for a'radicle 40
selected from the group consisting of the benzene
and phenyl-pyrazolone series, R2 means a radicle
of the benzene series and R1 and R2 contain at
least one member selected from the group con
sisting of hydrogen, —SO3Na and -—COONa,
which dyestuffs dye wool from an acid bath olive
green to green shades of excellent fastness and
possess a'f?nity to cotton too. I
2. The monoazo dyestu? of the formula:
0
50
NH:
bromo-anthraquinone-2-sulfonic acid, 30 parts
of the sodium salt of 4-amino-azobenzene-4'-sul
fonic acid, 20 parts of sodium carbonate and about
1000 parts of water are mixed and the mixture
in Or is heated to about 90 to 100° C. for about 12 hours
while stirring. The slightly soluble copper salt
of the condensation product formed precipitates
from the solution. It is ?ltered off and washed,
then dissolved in boiling water by means of hy
60 drochloric acid. From this solution the conden
sation product is isolated by the addition of
sodium chloride. It is ?ltered off, washed and
further puri?ed by dissolving in Water and pre
cipitating by means of ammonia. Then the new
dyestuff is ?ltered off, washed and dried. It cor
responds to the formula:
70
75
—SOaNa
Y
55
which dyestu?' is a greenish black powder, sol
uble in concentrated sulfuric acid with a violet
color, dyeing wool from an acid bath very fast
0
olive-green shades.
3. The monoazo dyestuif of the formula:
(I )
NHQ
SOaNa
65
which dyestuif is a greenish black powder, soluble
in concentrated sulfuric acid with a violet color,
dyeing wool from an acid bath very fast green
shades.
75
4
2,108,126
4. The monoazo dyestu? of the formula:
which dyestu? is a greenish black powder, soluble
in concentrated sulfuric acid with a reddish violet
color, dyeing wool from an acid bath very fast
green shades.
OOONa
/
O
ERNST HONOLD.
CARL TAUBE.
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