Патент USA US2607784

Patented Aug. 19, 1952
2,607,782
UNITED * STATES PATENT.‘ OFFICE:
PROCESS
TETRAAMINO-ANTHRAQUINONE
FOR THE PRODUCTION OF 1:4:5
George W. Seymour, Maplewood, and Victor S.
Salvin,‘Summit,“N. J., assignors tov Celanese
Corporation of America, a corporation of Dela
ware '
'
N0 Drawing. ApplieationSeptember 30, 1947, i
. Serial No. 777,120
'
6 Claims. (01. ‘260-378
1
This invention relates to the preparation of
anthraquinone dyestuffs and relates more par
ticularly to an improved process for the pro
the mixture of acetylated 1:5- and 1:8-diamino
anthraquinone employed during the preparation
of said dyestu? is effected at a reaction'tempera
1 :4 : 5 : 8-tetraamino-anthraquinone.
'ture of from 10 to 20° C’. in solution in a substan
An object of this invention is the‘ provision of
an improved process for, the production ’of
1 :415 : B-tetraamino -anthraq'uinone whereby said
dyestu?‘ may be obtained in increased purity and
tial excess of sulfuric acid. By effecting-the ni
‘ duction
of
yield.
I '
tration at atemperature of 10 to 20° C. substan
tially complete nitration of the acetylated 1:5
and' 1:B-diamino-anthraquinoriey'in the vfree
para-positions is achieved. Upon subsequent re
Another object of this invention is to provide 11 duction of the di-nitrated acetylated-diamino
intermediatev followed by hydrolysis of the acetyl
an improved process, for the production of
groups, 1:415:8-tetraamino - anthraquinone'of
1:4z5z8-tetraamino-anthraquinone which is ca
excellent dyeing properties is obtained. The use
pable of yielding dyeings on cellulose acetate or
of an excess of sulfuric acid, preferably, in an
other organic derivative of cellulose materials
the
in blue shades of increased light, fastness and 15 amount of from 5_ to 8 parts by weight
‘ possessing a neutral change in shade under arti
?cial
light.
'
_
I
weight of the mixture of acetylated 1:5; and 1:8
fdiamino-anthraquinone, acts to inhibitany pre
cipitation of the dinitro-diacetylamino~anthra
quinone formed. Where excesssulfuric acid is
Other objects of this invention will appear
from the following detailed description.
The anthraquinone dyestuff 1:4:5z8-tetra 20 present, precipitation 'of the nitrated product
formed duringithe ‘nitration reactionjis' mini
amino-anthroquinone, as heretofore obtained,
has been found to dye cellulose acetate or other
vmized and, therefore,‘ the occlusion of‘ any ‘in
' completely nitrated product in" such precipitate
organic derivative of cellulose materials in rather
is avoided. ‘ Since such pre'cipitationjis avoided
dull, reddish-blue shades which are not only
lacking in light fastness but, in addition, exhibit 25 any incompletely ‘nitrated product is retained in
solution for a su?icientjperiod to complete vthe
an undesirable change in shade when viewed
under arti?cial light. The dyestuff has been ob
. nitration.
,
tained by a sequence of steps involving thenitra
Thus, in ‘accordance, with our vnovelproc'ess,
the mixture of acetylated 1:5- and 1:8-diamino
‘tion of anthraquinone to a mixture of 1:5- and
1:B-dinitro-anthraquinone,
reduction
of » the 30
vnitro groups to the corresponding 1:5- and 1:8
diamino compounds, acetylation to protect the
free amino groups, followed by nitration, reduc
tion and hydrolysis of the acetylated 1:5- and
anthraquinone tobe nitrated is dissolvedin from
V5, to 8 parts byweight of concentrated, i. ,e'. 96%,
sulfuric acid on the weight of the anthraquinone
compound at a temperature of 10" to 15° ‘Cfan'd
then2 to 2.5 parts by weight of a mixture ‘of
1:8-diamino-anthraquinone isomers toyield the 35 ‘96% sulfuric acid and 65% nitric acid contain-
desired 1 : 4 : 5 : 8r-tetraamino-anthraquinone. The
undesirable characteristics of the dyestu?‘ ob
tained by this process appear to be due primarily
to incomplete nitration and amination of the
Jy
ing 0.5‘ to 0.75 vpart by weight of nitric acid .on
the weight of the intermediate are slowly added
thereto over about one hour. The temperature
of the reaction mixture is then raised slightly.
mixed acetylated 1:5- and, 1:8-diamino-anthra 40 to about 16 to 20° C., usually to about 18‘? C., and
maintained at this temperature _for 2 to 4 hours
to complete the nitration. The nitrated‘ prod
uct is precipitated from solution by drowning the
'quinone product with the result that the 1 :4:5:8
tetraamino-anthraquinone ?nally obtained con
,tains, an appreciable quantity of tri-amino
anthroquinone. Partial methylation of the ?nal
nitration melt in-a mixture of ice and waterand
'aminated product has been suggested as a means 45 the precipitated dinitro-acetylated .1-25- and 1:8
diamino-anthraquinone-is then ?ltered mi and
,of brightening the shade and shifting the color
Zirorn. the reddish-blue ‘shade obtained tov one
which is amore greenish-blue but the partially
methylated amino-anthraquinone dyestu?‘, while
somewhat more acceptable, stillis notentirely';60
satisfactory.
‘
.
washed free of acid. ,- Nitration in accordance
with our process yields a substantially complete
1y di-nitrated product.
'
Reduction “of the dinitro-acetylated 1-25} and
l : 8-diamino-anthraquinone to diaininoel: 5V and
. We have now found that 114:5:8-tetraamino
a 1 :8-diacetylamino-anthraquinone, prior. ' to ' hy
ianthraiquinonev substantially free of 'triamino
- drolysis of the acetyl groups, vis effected in aque
ous suspension‘ employing sodium sul?de as the
~anthraquinone and vof notably improved dyeing
properties Imay-be'obtained if the=nitration of. 55 reducing agent. =Reduction is ?rst-effected ata
2,607,782
4
' 3
150 parts by weight of mixed aceylated 1:5
temperature of about 20° C. for about 1 to 2
hours to reduce the nitro groups present to hy
droxylamine groups. The temperature of the
aqueous suspension is then raised over about 1
to 3 hours to 75 to 85° C. and is maintained at
said temperature for about 2 to 4 hours to com
plete the reduction of the nitro groups to the
and 1:8-diamino-anthraquinone are dissolved
at 10 to 15° C. in 1000 parts by weight of con
centrated 96% sulfuric acid and then 400 parts by
weight of mixed acid containing. 150v parts by
weight of 65 % nitric acid and 250 parts by weight
of 96% sulfuric acid are added slowly over about
1 hour at a temperature of 12 to 15° C. The
then ?ltered off and washed free of alkali solu- ' temperature is then raised to 18° C. for 4 hours
ble impurities.
l0 after which the nitration melt is drowned in
' desired amino groups. The reduction product is
5000 parts by weight of a mixture of ice and
The hydrolysis or de-acetylation of the di
. water causing the yellow dinitro-acetylated 1:5
amino - 1:5- and 1:8 - di - acetylamino - anthra
and 1:8-diamino-anthraquinone to precipitate.
quinone to 1:4:5:8-tetraamino-anthraquinone is <
> 'The yellow-solid is ?ltered off and washed free of
in concentrated, i. e. 90%, sulfuric acid and 15 acid. The wet press cake of dinitro-acetylated
1:5- and 1:S-diamino-anthraquinone is slurried
warming the solution at 80 to 90° C. for about 1 ,
effected by dissolving the acetylated compound
to 2 hours. The acetyl groups are split off and‘
the 1:4:5:8-tetraamino-anthraquinone is pre-'
cipitated by drowning the sulfuric acid solution
in a mixture of ice and water.
The precipitated
1:415:53 - tetraamino - anthraquinone is ?ltered
from/the supernatant liquid and washed free of
acid. The anthraquinone dyestu?.’ thus obtained
dyes cellulose acetate or. other organic derivative
of cellulose materials in very desirable blue shades
of good fastness .properties having a neutral
change in shade under arti?cial light. No partial
vmethylation of the dyestuff is required in. order
.to render the dyestu? commercially satisfactory.
In order further to illustrate our invention but
without being limited thereto, the following
1 into 2000 parts by weight of water and a solu
'tion of 250 parts by weight of sodium sul?de
in 700 parts by weight of Water is added to the
20 slurry at 25° C. The mixture obtained is then
stirred at 25° C. for 1 hour to reduce the nitro
groups to hydroxylamine groups, the reduction of
said groups being indicated by the formation of
a green-blue color. The temperature is then
to 75° C. over. 1 hour and then held. be
V25 raised
tween 75 and 80° C. for 2 hours to complete the
reduction to the desired. amino groups. There
duction product is then ?ltered off from the warm
suspension and washed thoroughly with water
30 until all of the alkaline water-soluble impurities
are washed out. The wet press cake is added to
400 parts by Weight of concentrated 90% sulfuric
- example is given:
2'08v parts by weight of anthraquinone are dis
acid and the solution obtained is warmed at
90° C. for 1 hour to effect the hydrolysis _or de
acetylation of the acetylamino groups. On
solved in 2000 parts by weight of concentrated,
drowning the sulfuric acid hydrolysis .mixture,
96% Sulfuric acid at 20 to 25° C. and then 470
parts by weight of mixed acid containing 240
in 1500 parts of a mixture of ice and. water,
1 :4 : 5 : 8-tetra-amino-anthraquinone precipitates
Example
parts by weightof 65%Vnitric acid and 230 parts
from solution. The 1:4:5:.81tetraamino-anthra
by weight of 96% sulfuric acid are added slowly 40 quinone is then ?ltered off and Washed free of
acid with water. A ‘70% by weight‘ yield of
'over. 2 hours, The temperature rises to 80° C.
1:4:5z8 - tetraamino- based on the mixed, di
due, to the exothermic nature of the reaction and
acetylamino-anthraquinones ‘is obtained. The
the mixture is then warmed to 955C. for 2 hours
to complete the‘ ‘nitration. After‘ cooling the
dyestuff dyes cellulose acetate or other ‘ organic
nitration mixture ‘to 25° C., the dinitro-anthra
quinone formed is precipitated from solution by
derivative of cellulose textile materials,_ for'ex
drowning in 'a mixture of ice and water.
ample, a blue shade of good light fastness having
a, neutral change in shade when exposed to ar
The
ti?cial 1ight._ Thedyestulf 'is commercially satis
factory in the-form obtained and no, partial
methylation' is necessary to render itvcommer
yellow dinitroanthraquinone which precipitates
isflltered andthenwashed free of acid. . 7 About
295 parts ‘by weightiof a mixture‘of 115-. and
v1':8i-dinitroanthraquinone is obtained. ‘The acid
50
cially acceptable.
'
'
,,
,
.7
" 'It is to be understood that the foregoing de
free wet press cake of 1 :5 and 1:8-dinitro-anthra
tailed descriptiongis given merely by Way‘ of
.quinone is then slurried into about 3000 parts by
1 illustration and'that many-variations may be
.weight'of water and a solutionyof 350. parts ‘by
“weight of sodium sul?de dissolved in 1000 parts
made therein-without departing from, the spirit
by weight of water is added to the suspension 55 of our invention.“
Having desc'ribedour invention,_g"wha't we desire
‘at 25° C. The slurry is stirred for‘ 1 hour at 20
"to'secure'by Letters Patent is z"
to 30° C. and the temperature is then raised over
1. In a process for the production of 1:4;5z8
about 1 hour to 85° C. and held at this temper
tetraamino - anthraquinone substantially free
ature for ‘2 hours to complete the reduction of
the dinitro compound to the-corresponding di .60. from triarnino-anthraquinone, which includes ni
trating a mixture’of'acetylated 1:5- and ‘1:8
The‘suspended 1:5- and
' amino-anthraquinone.
'l:8-diamino-anthraquinone is filtered off and
- diamino-anthraquinone, reducing the addednitro
washed thoroughly with water, about 200 parts
:groups, and then hydrolyzingme ‘acetylamino
by weight being obtained on drying. " The product
groups to form free amino groupspthe'step which
is‘ then suspended in a mixture of 400 ‘parts by
comprises effecting the‘ nitration offthe mixed
Iweight of acetic acid and 400 parts'by weight of
acetylated 1:5- and l:8-diaminoiantliraquindne
acetic anhydride and held at 130° C; for 3 hours
at a temperature of from 10 to 20?’ C. in a solution
during which time the solution changes from
a bright red to a yellow color, indicating the
containing a total o'fT6.0 'to- 9.6v partsTby weight (if
completion ' of ' thervacetylation "reaction.
The‘
. solution is then dropped‘. on to av mixture of ‘ice
- 100% sulfuric acid and about\0.6 part by weight
70‘
'
ofnitric acid on theweight of the anthraquinone
compound.
-
and water and the mixture ofrac‘etylated 1:5 and
2.'In a_ process vfor the'production bill-4151's-
1:8 - diamino - anthraquinone' precipitates. ‘as a
rtetraam'ino - 'anthraquinone' substantially :' free
yellow solid. :About 260 parts‘by weight of the
,iacetylated mixture are. obtained.
‘
"
>
' from tr1amino—anthraquinone which includes ni
trating a‘ mixture of ac'etylated 1:5,; and"1=:8
,
2,607,782
6
diamino-anthraquinone, reducing the added nitro
10 to 20° C. in a solution containing a total of
groups, and then hydrolyzing the acetylamino
groups to form free amino groups, the step which
comprises effecting the nitration of the mixed
acetylated 1:5 and 1:8-diamino-anthraquinone
6.0 to 9.6 parts by weight of 100% sulfuric acid
and about 0.6 part by weight of nitric acid on the
weight of the anthraquinone compound, precipi
tating the dinitro-acetylated 1:5- and 1:8-di
amino-anthraquinone from solution by drowning
at a temperature of from 10 to 20° C. in a solution
containing a total of 6.0 to 9.6 parts by weight of
100% sulfuric acid and about 0.6 part by weight
of nitric acid on the weight of the anthraquinone
the nitration melt in a mixture of ice and water,
reducing the nitro groups of the dinitro-acetyl
ated 1:5- and 1:8-diamino-anthraquinone to
compound and precipitating dinitro-acetylated 10 hydroxylamine groups with sodium sulfide while
1:5- and 1:8-diamino-anthraquinone from solu
in aqueous suspension at 25° 0., raising the tem
tion by drowning the nitration melt in a mixture
perature to '75 to 85° C. to complete the reduction
and hydrolyzing the acetylamino groups with
of ice and water.
3. Process for the production of 1:4:5z8
concentrated sulfuric acid to yield 1:4:5:8-tetra—
tetraamino - anthraquinone substantially free
amino-anthraquinone.
'
1
from triamino-anthraquinone which comprises
6. Process for the production of 1:415:8
nitrating a mixture of acetylated 1:5- and 1:8
diamino-anthraquinone at a temperature of from
10 to 20° C. in a solution containing a total of 6.0
tetraamino - anthraquinone substantially free
from triamino-anthraquinone, which comprises
nitrating a mixture of acetylated 1:5- and 1:8
diamino-anthraquinone at a temperature of from
to 9.6 parts by weight of 100% sulfuric acid and
about 0.6 part by weight of nitric acid on the
weight of the anthraquinone compound, precipi
tating the dinitro-acetylated 1:5- and 1:8-di
amino-anthraquinone from solution by drowning
10 to 20° C. in a solution containing a total of 8
parts by weight of 100% sulfuric acid and about
0.6 part by weight of nitric acid on the weight of
the anthraquinone compound, precipitating the
dinitro-acetylated 1:5- and 1:8-diamino-anthra
quinone from solution by drowning the nitration
melt in a mixture of ice and water, reducing the
nitro groups of the dinitro-acetylated 1:5- and
the nitration melt in a mixture of ice and water,
reducing the nitro groups and hydrolyzing the
acetylamino groups to yield 1:4:528-tetraamino
anthraquinone.
1:8-diamino - anthraquinone to hydroxylamine
4. Process for the production of 1:4:5:8
tetraamino - anthraquinone substantially free 30 groups with sodium sul?de while in aqueous
irom triamino-anthraquinone, which comprises
nitrating a mixture of acetylated 1:5- and 1:8
suspension at 25° 0., raising the temperature to
75 to 85° C. to complete the reduction and hydro
lyzing the acetylamino groups with concentrated
sulfuric acid to yield 1:4:5:8-tetraamino-anthra
quinone.
GEORGE W. SEYMOUR.
diamino-anthraquinone at a temperature of from
10 to 20° C. in a solution containing a total of
6.0 to 9.6 parts by weight of 100% sulfuric acid
and about 0.6 part by weight of nitric acid on the
weight of the anthraquinone compound, precipi
VICTOR S. SALVIN.
tating the dinitro-acetylated 1:5- and 1:8-di
amino-anthraquinone from solution by drowning
REFEREN
the nitration melt in a mixture of ice and water, 40
reducing the nitro groups of the dinitro-acetyl
ated 1:5- and 1:8-diamino-anthraquinone with
sodium sul?de while in aqueous suspension and
hydrolyzing the acetylamino groups with concen
trated sulfuric acid to yield 1:425:8-tetraamino
anthraquinone.
Number
45
2,309,708
from triamino-anthraquinone, which comprises
nitrating a mixture of acetylated 1:5- and 1:8 50
diamino-anthraquinone at a temperature of from
Name
\
Date
Olpin et al.‘_‘_ ______ __ Feb. 2, 1943
FOREIGN PATENTS
5. Process for the production of 124:5:8
tetraamino - anthraquinone substantially free
CITED
The following references’ are of record in the
?le of this patent:
UNITED STATES PATENTS
Number
127,780
Country 1
Date
Germany _‘ ________ __ Jan. 17, 1902
143,804
Germany _________ __ July 27, 1903