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Патент USA US2108142

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2,108,14
Patented Feb. 15, 1938
UNITED STATES PATENT OFFICE’
2,108,142
ACID WOOL DYESTUFFS
Heinrich Bitter, Frankfort-on-the-Main-Fechen
heim, Germany, assignor to General A_n1line
Works, Inc., New York, N. Y., a corporation of
Delaware
No Drawing. Application August 12, 1936, Se
rial No. 95,623. In Germany August 13, 1935
4 Claims.
(Cl. 260-64)
This invention relates to valuable new acid
wool dyestuffs, more particularly to those of the
general formula:
following examples are given, the parts being by
N03
wherein R1 stands for a member selected from
the group consisting of alkyl, cycloalkyl, aryl and
10
N02
Z stands for a member selected from the group
1
?bers various shades of Very good leveling power
and fastness properties, partly of an excellent
fastness to light, partly of an especially good fast
ness to washing, ironing, sea water and perspira
tion.
In order to further illustrate my invention the
consisting of S02, CO, SO2-aryl-SO2 and CO-aryl
CO, 11. stands for the number 1 or 2, X1 stands for
a member selected from the group consisting of
aryl-NH-aryl, cycloalkyl-NH-aryl.
(Aryl mean
ing in each occurrence of the above signi?cations
a radicle selected from the group consisting of the
benzene and napthalene series.)
The new dyestuffs are obtained by condensing
nitro compounds of the general formula:
weight and all temperatures in centigrade de
grees; but it is, however, to be understood that my
invention is not limited to the particular products
nor reacting conditions mentioned therein.
Example 1
28 .6 parts of the sodium salt of 4-amino-diphen
ylamine-2-sulfonic acid are dissolved in ten times 15
the quantity of water, 25 parts of l-chloro-Z-ni
trobenzene-ll-ethylsulfone, about 160 parts of al
cohol and 10 parts of sodium acetate are added
and the mixture is heated to boiling in an ap
paratus provided with a re?ux condenser for
some hours. Then the alcohol is distilled oil and
the dyestu? formed is separated from the aqueous
solution by evaporation or addition of sodium
chloride.
The new dyestu? thus obtained of the formula:
25
NO;
wherein R2 stands for a member selected from
30 the group consisting of alkyl, cycloalkyl, aryl and
X:
No;
35 X2 stands for a member selected from the group
consisting of halogen and alkoxy, and Z has the
above said signi?cation, with compounds of the
general formula:
N02
SOaNa
dyes Wool from an acid bath yellowish brown
shades of very good levelling power and excellent
afastness to light.
,
>
The same dyestu? is obtained by starting from
1-methoxy-2-nitrobenzene-4-ethylsulfone instead
of the 1-chloro-2-nitrobenzene-4—ethylsulfone in
35
the above example.
The corresponding dyestu? prepared according
to Patent No. 1,059,571 by starting from 2,4-dini
tro-chlorobenzene is considerably surpassed by
the new dyestu?' as regards levelling power’ and
40
25
fastness to light.
5 O the like in an aqueous medium or in an organic
phenylamine-Z-sulfonic acid are dissolved in ten 50
times the quantity of water, 26.3 parts of 1
diluent with or without the simultaneous addi
tion of water either in an open vessel provided
with a re?ux condenser or in a closed vessel un
der pressure.
55
The new dyestuffs thus obtained .dye animal
'
40
wherein X1 and n have the above said signi?ca
tion. (Aryl meaning in each occurrence of the
above con?guration a radicle selected from the
group consisting of the benzene and naphthalene
45 series.)
The condensation may be carried out by heat
ing the initial materials in the presence of acid
binding agents such as for example sodium ace
tate, calcium hydroxide, calcium carbonate and
By employing 33 parts of the sodium salt of
4’- ethoxy-ll-amino - diphenylamine - 2 - sulfonic
acid instead of the sodium salt of 4-amino-di
phenylamine-2-sulfonic acid in the above exam
ple a similar brown dyestuii of likewise good prop
erties is obtained.
4:5
‘ 1
Example 2
28.6 parts of the sodium salt of 4-amino-di
chloro-2-nitrobenzene-4-propylsulfone
and
10
parts of sodium acetate are added and the mix
ture is heated to boiling for some hours in an
apparatus provided with a re?ux condenser. 55
2
2,108,142
Then the dyestu? formed is separated from the
sodium acetate and about 240 parts of alcohol
are added and the mixture is heated to boiling
for some hours in an apparatus provided with a
re?ux condenser. Then the alcohol is distilled
solution by evaporation or addition of sodium
chloride.
The new dyestuff thus obtained of the formula:
CHaCHzCHnSOrQNH-QNH—®
N Oz
solNa
dyes wool brown shades, darker brown than those
of the dyestuff obtained according to Example 1,
and of likewise good levelling power and fast—
ness to light.
o?, the aqueous solution is ?ltered and the dye
stuiT formed is separated from the ?ltrate by
the addition of sodium chloride.
The new dyestuff thus obtained of the formula:
15
NaOaS
By employing 27.5 parts of 1-chloro-2-nitro
benzene-‘l-butylsulfone instead of the l-chloro
2-nitrobenzene-4-propylsulfone in the above ex
dyes wool from an acid bath yellowish brown
shades of excellent fastness properties.
20 ample an analogous dyestu? is obtained which
Example 5
dyes wool full brown shades of likewise good
fastness properties.
Dyestuffs of similar properties are obtained by
replacing the sodium salt of 4-amino-dipheny1
25 amine~2-sulfonic acid employed in Examples 1
and 2 for example by the sodium salts of 4
31.6 parts of the sodium salt of ¢l'-methoxy-4
amino - 4’ - acetylannno-diphenylamine - 2 - sul
30
zene-B-sulfonic acid and the like.
Example 3
28.6 parts of the sodium salt of Ll-amino-di
pheny1amine-2-sulfonic acid are dissolved in ten
times the quantity of water, 27 parts of 1,6-di
chloro-2—nitrobenzene-4-methylsulfone at 149°
melting point and 10 parts of sodium acetate are
added and the mixture isvheated to boiling for
some hours in an apparatus. provided with a re
?ux condenser. Then the solution is freed from
45
impurities by ?ltration and the dyestu? formed
is separated from the ?ltrate by evaporation or
addition of sodium chloride.
The new dyestu? thus obtained of the for
mula:
Example 4 with 18.8 parts of 4,4’-dichloro-3,3'
dinitro-diphenylsulfone in the presence of 5 parts
of magnesium oxide.
The new dyestu? thus obtained of the formula:
30
N 02
fonic acid, 1-amino~4-cyclo-hexylaminobenzene
3-sulfonic acid, 1-amino-4-naphthylamino-ben
'
20
amino-diphenylamine-2-sulfonic acid are con
densed in an analogous manner as described in
/
OgN
NaOaS
15
SOaNa
SOaNa
dyes wool from an acid bath brown shades of ex
cellent fastness properties.
An analogous dyestu? is obtained by employing
33 parts of the sodium salt of 4'-ethoxy-¢l-amino- ' '
diphenylamine-2-sulfonic acid instead of the 31.6
parts of the corresponding 4’-methoxy compound
in the above example, whereas the dyestu? pre
pared by employing the corresponding amount of
3'4’-dimethoxy-4-amino—diphenylamine - 2 - sul
40
ionic acid dyes considerably deeper brown shades.
Example 6
28.6 parts of the sodium salt of 4-amino-di
phenylamine-Z-sulfonic acid, about twenty times _
the quantity of a mixture of water and alcohol
which mixture contains 50% of alcohol, 28.3 parts
of
naphthalene-1,5-di-(3’-nitro-¢l’-chlorophen
yl) -sulfone of 306-30'7° melting point and 10
parts of magnesium oxide are heated to about 50
50
140 to 150° for some hours in an autoclave pro
vided with a. stirrer. Then the sodium salt is
’
NO;
\soaNa
dyes wool from an acid bath yellowish brown
shades.
By
employing
the
corresponding
amounts of the sodium salts of 4’-methoxy-4
amino—diphenylamine-2esulfonic
acid
or
ethoxy-4-amino-diphenylamine-2-sulfonic
,NaOaS
65
4’
acid
olN
tion or addition of sodium chloride.
The new dyestu? thus obtained of the formula:
times the quantity, of water, 18.8 parts of 4,4’
dichloro-3,3’-dinitro-diphenylsulfone, 10 parts of
QNH-Q
SOrQNH
NOI
instead of the sodium salt of 4-aminodiphenyl
amine-Z-sulfonic acid in the above example dye
stu?s are obtained which dye more reddish brown
shades of similar properties.
Example 4
28.6 parts of the sodium salt of 4-amino-di
phenylamine-Z-sulfonic acid are dissolved in ten
75
formed by the addition of the corresponding
amount of sodium carbonate, the alcohol is dis
tilled off, the aqueous solution is freed from im 55
purities by ?ltration while hot and the dyestuff
formed is separated from the ?ltrate by evapora
SOaNB.
dyes wool from an acid bath brown shades of
65
good fastness properties.
Analogous dyestuffs are obtained by employ
lng instead of the sodium salt of Il-amino-di
phenylamine-2-sulfonic acid in the above ex
ample the sodium salts of the corresponding 4’
methoxy or 4'-ethoxy compounds or the like.
Example 7
632 parts of the sodium salt of 4'-methoxy-4
70
175
2,108, 142
amino-diphenylamine-Z-sulfonic acid, 41 parts of
3,3’ - dinitro - 4,4'5' - trichloro-diphenylsulfone,
about twenty times the quantity of a mixture of
water and alcohol which mixture contains 50%
of alcohol, and 20 parts of sodium acetate are
heated in an apparatus provided with a re?ux
condenser or in a closed vessel under pressure,
until the formation of the dyestu? is complete.
Then the alcohol is distilled o?, the aqueous so
10 lution is freed from impurities by ?ltration and
the dyestu? formed is separated from the ?ltrate
by evaporation or addition of sodium chloride.
3
ten times'the quantity of water, 17 parts of
4,4’-dichloro-3,3'—dinitro-benzophenone, 10 parts
of sodium acetate and about 160 parts of alcohol
are added and the mixture is heated to boiling
for some hours in an apparatus provided with
a re?ux condenser. Then the alcohol is distilled
off, the aqueous solution is freed from impurities
by ?ltration and the dyestuff formed is sepa
rated from the ?ltrate by the addition of sodium
chloride.
The new dyestufi thus obtained of the for
mula:
15
15
SOQNB.
NaOsS
The new dyestu? thus obtained of the formula:
dyes wool from an acid bath yellowish brown
20
20
SOaNa
NaO;S
dyes wool from an acid bath yellowish brown
shades of good fastness properties.
An analogous dyestuff is obtained by employ
ing instead of the 41 parts of 3,3’-dinitro-4,4’5’
trichloro-diphenylsulfone in the above example
the corresponding amount of 3,3'-dinitro-5
30
methyl-4,4’?-trichloro-diphenylsulfone.
Example 8
28.6 parts of the sodium salt of 4-amino
diphenylamine-Z-sulfonic acid are dissolved in
ten times the quantity of water, 20 parts of 4
chloro-3-nitro-acetophenone and 10 parts of
sodium acetate are added and. the mixture is
heated to boiling for some hours in an appara
tus provided with a re?ux condenser. Then the
solution is ?ltered and the dyestuff formed is
separated from the ?ltrate by evaporation or
addition of sodium chloride.
shades of good fastness to washing, light and
perspiration.
Similar dyestuffs of likewise good fastness 25
properties are obtained by employing 31.6 parts
of the sodium salt of 4’-methoxy-4-amino-di
pheriylamine-Z-sulfonic acid or 34.3 parts of the
sodium salt of 4’-acetamino-4-amino—diphenyl
amine-Z-sulfonic acid or 34.6 parts of the sodium
salt of 3'4’~dimethoxy-‘i-amino-diphenylamine
2-sulfonic acid instead of the 28.6 parts of the
sodium salt of 4-amino-diphenylamine-2-sul
ionic acid.
35
Example 10
By condensing 28.6 parts of the sodium salt of
4-amino-diphenylamine-2-sulfonic acid with 21.6
parts of 4,4’-dich1oro-3,3',5,5'-tetranitro-benzo
phenone in the presence of 5 parts of magnesium 40
oxide in an analogous manner as described in
Example 9 a dyestu? is obtained of the formula:
N02
OzN
45
45
N09
NaQsS
The new dyestu? thus obtained of the formula:
50
I
SO3Na
NO:
dyes wool from an acid bath yellowish brown
shades of very good levelling power and fastness
to light.
By employing instead of the 28.6 parts of the
sodium .salt of 4-amino-diphenylamine-2-sul
fonic acid in the above example 33 parts of the
sodium
salt
of
4’-ethoxy-4-amino-diphenyl
60 amine-2-sulfonic acid a dyestufE is obtained
which dyes Wool somewhat more reddish brown
shades of likewise good fastness properties.
4-ch1oro-3-nitro-acetophenone is prepared by
nitration of 4-chloro-acetophenone by means of
65 mixed acid in concentrated sulfuric acid at about
0 to 10°. It crystallizes from methylalcohol in
colorless crystals of 90 to 91° melting point.
SOaNa
which dyes wool from an acid bath yellowish
brown shades of very good fastness to washing
and perspiration.
A somewhat more reddish brown dyeing dye
stuff is obtained by employing 31.6 parts of the
sodium salt of 4’-methoxy-4-amino-diphenyl
amine-Z-sulfonic acid instead of the sodium salt
of 4-amino-diphenylamine-2-sulfonic acid in the 55
above example.
Example 11
33 parts of the sodium salt of 4'~ethoxy-4=
amino-diphenylamine-2-sulfonic acid are dis
solved in ten times the quantity of water, 22.3 60
parts
of
1,4-di-(4’-chloro-3’-nitro-benzoyl)
benzene, 10 parts of sodium acetate and about
160 parts of alcohol are added and the mixture
is heated to boiling in an apparatus provided
with a reflux condenser, until the formation of 65
dyestuff is complete. Then the alcohol is dis
tilled off and the dyestu? formed is separated
from the aqueous solution by the addition of a
Example 9
70
10
28.6 parts of the sodium salt of 4-amino
diphenylamine-2-sulfonic acid are dissolved in
little amount of sodium chloride.
The new dyestui‘f thus obtained of the for
mula:
70
NEG-‘061115
75
N 25058
OzN
.
N02
SOzNa
75
4
2,108,142
dyes wool from an acid bath yellowish brown
shades of good fastness properties.
1,4-di- (4’-chloro-3'-nitro-benzoyl) -benzene is
prepared by nitrating by means of mixed acid
Iclaim:
1. The acid wool dyestuffs of the general
formula:
at about 30 to 40° in monohydrate the con
densation product which is obtained according
to the method of Friedel-Crafts by acting with
10
terephthaloyl chloride on mono-chlorobenzene.
wherein R1 stands for a member selected from
It crystallizes from glacial acetic acid in color
the group consisting of alkyl, cycloalkyl, aryl and
less crystals of 180-187“ melting point.
10
Example 12
28.6 parts of the sodium salt of e-amino-di
phenylamine-Z-sulfonic acid are dissolved in ten
times the quantity of water, 26.8 parts of 1,4
di- (4’-chloro-3’5'-dinitro-benzoyl) -benzene, 10
parts of sodium acetate and about 160 parts of
alcohol are added and the mixture is heated to
boiling for some hours in an apparatus pro
20 vided with a re?ux condenser. Then the alco
hol is distilled off, the aqueous solution is freed
from impurities by ?ltration and the dyestuff
formed is separated from the ?ltrate by the
addition of a little amount of sodium chloride.
The new dyestuff thus obtained of the for
mula:
Z stands for a member selected from the group
consisting of S02, CO, SOi-aryI-SOz and CO—ary1— 15
CO, n stands for the number 1 or 2, X1 stands
for a member selected from the group consisting
of aryl-NH-aryl, cycloalkyl-NH-aryl (aryl mean
ing in each occurrence of the above signi?ca
tions a radicle selected from the group consisting 20
of the benzene and naphthalene series), which
dyestuffs dye animal ?bers various shades of very
good levelling power and fastness properties,
partly of an excellent fastness to light, partly of
an especially good fastness to washing, ironing, 25
sea water and perspiration.
NO:
NEG
30
NaOJS
NO:
dyes wool from an acid bath yellowish brown
shades of very good fastness to washing and
perspiration.
By employing instead of the 28.6 parts of the
sodium salt of 4-amino-diphenylamine-2-su1fonic
acid in the above example the corresponding
amount of the sodium salt of 4'-eth0xy—4~ami—
no-diphenylamine-2-sulfonic acid a dyestuif is
obtained which dyes wool somewhat more reddish
brown shades of likewise good properties.
30
SOaNa
2. The dyestu? of the formula:
CHa-CHrCHa-SOQNHO-NHO
35
\
No,
SOBNG
which dyestuff dyes wool from an acid bath brown
shades of very good levelling power and excellent 40
fastness to light.
~
3. The dyestu?f of the formula:
45
45
SOsNa
/
1,4-di- (4'-chloro—3'5'-dinitro-benzoyl) -benzene
which dyestuff dyes wool from an acid bath yel
is prepared by nitrating by means of an excess of
lowish brown shades of excellent fastness proper
mixed acid in fuming sulfuric acid, containing
ties, especially to washing, ironing, seawater and
50
perspiration.
50 25% of S03, at about 110-120° the condensation
product which is obtained according to the meth
NaOzS
0d of Friedel-Crafts by acting with terephthaloyl
chloride on monochlorobenzene. It crystallizes
from monochlorobenzene in colorless crystals of
219 to 220° melting point.
4. The dyestu? of the formula:
NO:
SOaNa
which dyestuff dyes wool from an acid bath yel
lowish brown shades of good fastness to washing,
light and perspiration.
HEINRICH RITTER.
60
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