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Patented‘ June 28, 19:38
; 2,121,928
2,121,928’
VANTHRAQ‘UIINONEQDYESTUFFS AND moo;
l
ESSFOR THEIR MANUFACTURE
1'
Albin Peter, Basel, Switzerland, assignor to the
Works, formerly Sandoz, Basel,’
'
' ?rm Chemical
I‘
'Switzerlandw-
'
' v1IN51Drawing. “Application'Maréh‘ >13,- 1935.; se
‘_
rialiNo. 10,938.,TIn Germany March 21, 1934 . -'
I is Claims.
The present invention relates to- new anthra
quinone dyestu?'s and vto aprocess for 'theiriman
ufacture. '
.
‘It has been found“ that new valuable dyestuffs
5 of the anthraquinone series can bepreparedby
(01. 260-60), ,1
_
‘
,
I
.
_
con?gurationis generally carried out in presence
of a solvent and a catalyst, at temperatures be‘
tween 50° and 250° 0., and in an open or in ‘a
closed vessel. As suitable-solvents the following,
‘or mixtures thereof, can be used: water, ethanol, 1
‘ condensing aromatic amines of the general ' methanol, chlorobenzene,.nitrobenzene, dimeth
ylaniline, phenol, glacial acetic'acid and the 0,0
formula
disubstituted aromatic bases themselves, when
N H2
v10
, they are used in excess. ., _
X
.
2
condensation in an inert atmosphere, for exam?
wherein X and Y represent alkyl and halogen and
Z represents hydrogen, alkyl, halogen or alkoxy,
'With such anthraquinone compounds that con
tain at least one group replaceable by an aro~
matic amine. "
.29
__J
‘
a
.
'
’
'The aromatic amines useful for the production
of the new anthraquinone dyestuffs are for ex
ample 1,-amino-2,4,6-trimethylbenzene, l-amino
' 2,6-dimethylbenzene; v1-amino-2,4-dimethyl- 6 -
bromobenzene, l-amino-6e-ethyl-2,4-dimethylben
25
zene or the like.
‘
'
_,
.
.
As anthraquinone compounds ‘which can, be
used in the present process, the following maybe
listed:
>
.
,
.
The alphaaminoanthraquinones, their homo
.30 logues and derivatives, halogenated in an (at-posi
tion, such as l-amino-4-bromo-anthraquinone,
1 - amino-4-chloro—anthraquinone,
l — amino - 2
methyl-4-bromo-anthraquinone, l-amino-2-sul
pho-4-bromo-anthraquinone,. 1-methylamino-4
35 bromo-anthraquinone, 1-amino-2,5-disulpho- or
2,8-disulpho-4-bromo=anthraquinone, l-amino
Z-ca'rboxy-é-bromo-anthraquinone,
l - amino¢2'
cyano-4-bromo-anthraduinone, l-amino-5l-chlo
ro-anthraquinone, 1-amino-2-methoxy-,4-bromo
anthraquinone,
I
copper
7 As catalyst
salts: are.
generally
used, but it is alsopossible to
carry out the condensation ‘in absence of copper.
, Sometimes it, is advantageous to carryout the
l - amino - 2-phenoxy-4-bromo-' ~
anthraquinone and so on.
,
‘Further, the mono- and dihalogenanthraqui
nones containing at least one halogen‘atom in an
deposition and their substitution products such
45 as 1amino-2,4:dibromo-anthraquinone, l-amino
ple in nitrogen or carbon dioxide atmosphere, 15
preferably under addition to the reaction mixture ,
of acid-binding agents, such as sodium-Q DOt'ase
sium- or ammonium-acetate, sodium- or potas
sium-carbonateor bicarbonate, soap and the like.
The condensation products obtained according
cellulose esters and ethers.
'
_. ‘ ‘
'
‘If it isv intended to obtain water-soluble dye I25
stu?s,j the condensation products obtained as
above described are subjected to, a sulphonation
process, whichmay be carried outby different
methods. If the condensation products contain
in their moleculea group that can be replaced
by the sulphonic acid group, as isthe case in the
p-halogen derivatives, then they are transformed
into water-soluble dyestuffs by heating them with
sulphites, whereby the halogen becomes replaced
by the sulphonic acid group. 3
.~
But it is possible to prepare .water soluble dye
stuffs from water-insoluble condensation prod
ucts by sulphonating 'them with sulphuric acid
or fuming sulphuric‘acid of an appropriate. con
quinone nucleus. It isf’alsopossible to combine
both sulphonation methods, that is the direct sul
phonation in the aryl nucleus and the subsequent
quinone, 1,4- or 15- or 1,8- or 1,7- or 1,6-dichloro
anthraquinone, l-chloro-anthraquinone, 1,3-di
the usual manner.
1-amino-2,4-dibromo-5-chloro-anthra
1
5,0 bromo-anthraquinone.
Further, the derivatives of, 'u-hydroxyanthra
quinones, such as the leuco-lAedihydroxyanthra
quinone.
_
1
‘
Finally, the anthrapyridones containing at
5,5 least one halogen atom in an a-position, such as
N-methyl-ll-bromo-anthrapyridone, C-‘carbeth
435
centration of S03 or with chlorosulphonic acid, 540
whereby one orrmore sulphonic acid groups .will
be introduced into thearyl or into the anthra
introduction of sulphonic‘ acid group by the sul
phite method. These sulphonation methods are
well known in the art and canbe carried out in
. 5- or -6- or -'7- or -8ésulpho-2,4-dibromo-anthra
' quinone,
20
to the presentprocess are, when-they arenot
sulphonated, valuable compounds for ‘(the dyeing
of lacquers,‘ like nitrocellulose lacquers, or of
'
By subjecting the sulphonated or unsulphon
ated condensation products containing a free 7
p-po'sition to the imino1 group in the aryl radical to
theaction of aldehydes such as formaldehyde,
acetaldehyde, benzaldehyde, benzaldehyde-dir
sulphonic acid etc. in an acid or neutral medium, 55
di- and triarylmethane derivativescan be pro
oxy- or C-acetyl-2-methyl-4-bromo-anthrapyri
duced.
done, or 2,é-dibromo-anthrapyridone.
The condensation of the anthraquinone deriva
pounds with oxidizing agents such as nitric acid',
By treating the above mentioned com
peroxideof manganese and the like, they yield
tives with the aromatic bases of the above cited valuable diaryl derivatives of theanthraquinone
60
2,121,928
2 .
series. By subjecting'the condensation products
‘ :_ Example 1;
containing at least one free a-amino group to the
.710 parts of C‘;carbethoziy-Z-methybfl-bromo
action of amides of carbonic acid, or to‘ the ac
anthrapyridone are heated half an hour to
tion of ‘esters of acetoacetic or malonic acid an; —~15_Q°-160° C‘. under stirring with 30 parts of 1- '
thrapyrimidones and anthrapyridonescan be ob
tained.
Q
amino-12,456-trimethylbenzene, 4 parts of potas
V_
si-urnacetate and‘; 0:51:- part of copper powder. '
The dyestuffs prepared according tojtheprocj-ii
After the'condensation is terminated, the reac- '
esses cited above are, when they are soluble in jtionmass'is allowed'jto cool down to about 100'”
water, very valuable dyes'tu?sior animal: _f1bres'_
diluted- with 50 parts of ethanol and allowed
10 such as wool and natural silk. TheIuse-of the . to'crystallizeij Theéprecipitate thereby obtained
aromatic amines substituted in both oepositions is ?ltered,wwashe_d_?rstwith ethanol and there
to the amino group allows? toi'idbtain dyestuffs‘ "on ' with water .andidried.
with very‘ pure and brilliant‘shadeszandriof .Vex—. . " ‘The intermediate product obtained.’ in this
cellent fastness properties.
>
v.
..
.
u
‘ ' manner. isathen sulphonated with weak oleum at
One object of the present invention ‘is there;
15
about 20° Q-and the sillphonation rmxturerzmlred
fore, theanthraquinone {dyestuffs containing in
théir'smolecule at least'o'ne group
-
-
on ice. ‘ The soluble dyestuffjtherebyjobtainedvis
'
then isolated in the usual manner.
It dyeswool
' a. brilliant. .rediylellow shade of ‘ excellent?fasté
ness to milling and. to’ perspiration;
20
It pos- _
sesses the formula ’
o
.
wherein X and}? represent haloéénlelndjalkvl,
is Y represents hydrogen and a ‘sulphogroupL-and
25
Z represents hydrogen, halogen, alkyl and alkoxy.
'sulpho and a linkage binding two of, such ‘group;
-CI-VI— phenyl and by ordinary linkage ‘between
30
the G-atoms offboth nuclei.
. V
H .
7
I30
,
Another object of the present invention isrthe
process for the ,manufactureoi anthraguinone
'dyestuifs,
consisting _ in . condensing V vanthr'aqui-r
none
derivatives,
with
.the above benzene
listed’ o,o,—di
substituted
aromatic
am'ines-ofthe
series.
7
Still ‘another object of the?’ present invention
CH3’
7
‘
‘_
A dyestu? of similar shade can be obtained if
‘the 1‘amino'zA’s‘tnimethylbenzene "is replaced
by an; equivalent _.quantit_y, of‘ l-Qamino-ZA-di
methyl-?-bromobenzene.
'_
r
"
"
.
'
is the'process, ior'thecondensation of the anthra
quinone ' derivatives with, the QOp-disubstituted
aromatic ‘amines of the benzene series, consisting '
20 parts of ‘bl-methyl-el-brorno-anthrapyri
in that the condensation is carriedoutin pres
done, 8 parts of potassium acetate',;0.1 part of 540
ence of solvents or diluents and catalysts, such copper powder and "70 parts of .1-amino-2,6-di
as copper or copper salts, and inpresence of 'methylbenzene areiheated up to 1'50°-‘160° C,,
acid-binding agents and at temperatures'between
50°
[45
and 250°
vC.
,_
V. ,
‘
_
.
‘.
Still another objectoithe Vpresentinvention,
‘is the condensation process,_ wherein as acid-'
binding agents an excessof the.o,o-disubstituted
.aromatic amines of ,thejbenzene series is used.
Still another object of the presentinvention
is the process of transforming .the water-insolu
ble condensation products ' of
anthraquinone
derivatives with the o_,o-d_i_substituted aromatic
amines into water-soluble ‘dyestuffs, ‘by treating
them with sulphonating agentasuchgas sulphuric
until the condensation is ?nished, what general
ly occurs after 2 to 3‘ hours. The reaction mix
ture is then allowed to cool down, diluted with
‘100 ‘parts of methanol and the precipitated base
separated by ?ltration.
'
'
v
’ Thevproduct thereby obtained is then sulphof
,nated with weakoleum and the dyestuff thereby
obtained isolated‘ in the usual -manner. ‘It dyes
animal, ?bres scarlet shades of excellentfast
__nesses and possesses the. formula
‘
55.5 acid or fuming sulphuric acid or sulphites. 7
55
7 Still another object of therpresent invention '
is the process .of ‘transforming the condensation
productsof the anthraquinone series into corre
sponding anthrapyridones or anthrapyrimidones
160 by treating them with esters. of aceto-acetic or
malonic acids or with amides of carbonic acid.
Still another object of the ‘present invention
is the process for transforming the-condensation
[products of the anthraquinone',‘seriesnobtained
1165 as above described into diphenyl-compounds or
V_
.C
a
.
V
.
Example 3
into diphenyl- and.triphenylmethane-compounds’
V 20 parts of l-methylaminoA-bromo-anthra
of the anthraquinone series, .by treating ‘such
'quinone are mixed with 6 parts of potassium
condensation products that, contain "a _free p_
acetate, 0.1 part of copper powder and '70 parts
of 1—amino-2,?-dimethylbenzeneV and heated up
position to the‘imino groupin the nucleus of the
to lo,o-disubstituted aromatic base, with oxidizing
agents or with aliphatic or with aromatic alde
hydes.
"
r
1 The following examples, without being limita
"tive, illustrate the present‘ invention, the parts
‘being ‘by ‘weight.
‘
‘ ‘
'
to 158° to ‘160? C. during ,2 to 3 hours. "The re
"ac'tion'm‘ass isthen allowed to cool down, diluted
'with "100 parts of methanol and the precipitated
condensation ‘product isolated ‘by ?ltration. The
lbasethereby obtained can‘be'used as .dyestuff for
‘lacquers or,-when sulphonated with weak oleum,
70
:3
2,121,928
7 Example 6
as acid dyestu? which dyes wool'brilliariti'red
2'01p‘arts of glacial aceticjacid, 22 parts of a
‘concentrated aqueoussolution of ammonium hy
dish-blue shades with good properties.) -' i1 i
‘The idyestuff thus obtained possesses the for.
mula
‘
'
'
droxidle, 40 parts "of water, 20 parts of l-amino
a: -2,4-dibromoanthraquinone, 0.2 part of copper
powderland 100' parts of l-amino-2,6-dimethyl
‘
5
benzene are heated on a re?ux during 24 hours. >
On dilution with 100 parts of ethanol, the base
precipitates in form of violet needles and is iso-.
pm:
,lpart of this base isv heated with 2 parts of an
. anti-10H;
aqueous solution of potassium sulphite (50%)
I’ 2 >.
,By'treating thejbasefaboveobtained- with urea
in presence of phenol 'assolvent, an anthrae
pyrimidone will be obtained, which on sulphona
vtion yields a water-soluble dyestuff dyeing wool
bluish-red shades.
'
1
.e
In thev same manner'dyestuffs from 1¢hy
20
ldroxy-4ébromo-anthraquinone and 1-amino-.2,6
and 4 parts of phenol during 16.hours at 140° C.
and after this time phenol is-separated from the .
reaction mixture by blowing it out by meansof
water steam. The solution thus remaining is
then ?ltered and the dyestu? is salted‘ out.
The dyestuff dyes; animal ?bres a brilliantred
dish-blue shade and possessesthe formula
‘N112
dimethylbenzene or other 0,0-disubstituted aro
matic ‘amines can be prepared.
'
‘
v:20
'
'
Example 4
10 parts of l-amino-2-methyl-4e-bromo-an
thraquinone, 30 parts of 1-amino-2,4,6-trimeth
525
ylbenzene, 4 partsof potassium acetate and 0.1
’ part of copper powder'are heated up‘ to 150°-160°
.C., until the condensation is complete and the
‘base thereby produced is then isolated as above
O described. On sulphonation of the base with
‘oleum, a dyestuff isv obtained dyeing wool' level
and brilliant violet-blue shades of excellent fast
ness to light and milling. Thedyestuff possesses
'
:35
the formula
NR2
I
'
'
$40
.
CH3
’
, By replacing the 1-amino-2,6-dimethylbenzene
by
1-amino12,4,6-trimethylbenzene, ' a
similar
dyestuifwwill be obtained, which possesses ex
cellent vfastness properties. By sulphonating
these ‘dyestuffs with sulphuric acid or oleum, new‘
dyestuffs containing two sulpho groups will be
obtained. They are easierv soluble in water, give
redder shades and can be used for printing pur
poses‘
Example 7
150 parts of water, 50 parts of ethanol, 20 parts
of the sodium salt of l-amino-‘l-bromo-anthra 40
' quinone-Z-sulphonic acid, 10 parts of sodium bi
7
7
‘-
45'
50
'
\
cm
carbonate, 02 part of copper powder and 40 parts
.
S0311.
Example. 5
of 1-amino-2,6-dimethylbenzene are heated to
gether during 10 hours on a boiling water bath.
The ethanol and the excess of: the aromatic base 945
are thereupon driven 01f by means of water steam
20 parts of 1,4-dichloro-anthraquinone, v18
parts of potassium acetate, 0.1 part of copper
powder and '70 parts of l-amino-2,6-dimethyl
and the dyestuff obtained is precipitated by means
benzene are heated to 170°-180° C., until the
shade of'the reaction mixture does no more
dyestuff prepared'asdescribed in Example 6.
change and after cooling down to about 100° C'.,
the condensation product is isolated in the man
ner above described."
-
’
i a By 'sulphonating the base with'weak‘ oleum at
of an addition of salt.
It is identical with the
15 parts of this dyestu? are dissolved in 180
parts of sulphuric acid of 93% and partially pre
cipitated by addition of 65 parts of water. To
the suspension thus obtained there are added 1.6
parts‘ of a formaldehyde solution‘ of 40% and the
40° C. a dyestuif is obtained which dyes wool. mixture is heated for three hours at>80° C. After 55
this time, a test ‘shaken with cold water shows
that the dyestuff has become insoluble. ' The
Its formula is:
CH3.
-‘ crystalline suspension is then ?ltered, the pre
cipitate is mixed with a small quantity of water,
EN;
\
neutralized with hydroxide of sodium or potas
60
sium, ?ltered and dried. The dyestuff thus ob
brilliant reddish-blue shades of excellent fast~
ness to light, milling, perspiration-and chromirre.
/o0\
6H3
S0311
tained dyes wool or natural silk from an acid or
neutral dye bath brilliant reddish-blue shades.
CO
.
CH:
|
The wool dyeings possess excellent fastness to
803K
milling, washing, potting and to light.
This dyestuff has the following formula:
HN—
NH:
65
NHz
CH3
By replacing the 1-amino-2,6-dimethylbenzene
/ /
HOaS-r
70
70 by 1-amino-2,4,6-trimethylbenzene, a similar dye
stuff will be obtained.
~
’
By using 1,5-dichloro-anthraquinone instead
of the 1,4-compound, a red dyestuff » will be ob
tained, which gives on wool dyeings of very good
1175 fastness to milling and'to light.
'
?
'
.
/
CH3
I
HNeQ-CHQNH
CH7!’
CH:
"
cO
Instead of treating the sulphuric acid solution
of the dyestuff with formaldehyde, it is possible
to treat it‘ with peroxide of manganese, whereby
.ter .this'time it-has been transformed into ;a bet
ter solubledyestu? of the formula
.
‘
/
v,
7
NHg
.
‘ '
.
a 'diphenyl derivative of/the formula
15031.3.
.
110s
.10
(I333
,
‘
v_
‘
eN~Q¢Hs
'
"
i-
OH.
10
.
dyeing wool pure blue shades of excellent fast
ness properties. Thisdyestuff can also be used
15 will be obtained.
This dyestuff possessessimilar
properties to those of the.diphenylrnethanev com
pound, prepared as above described.
'
Example 8
20
A mixture'consisting of 20 parts of ethanol,
19 parts of glacial acetic- acid, 24 parts of an
aqueous ammoniumrhydroxide solution (d:0.91),
80 parts of l-amino-6-ethyl-2,4-dimethylben
zene, 20 parts of l-amino-2,4-dibromo-anthra
in the printing’industryas.it,possesses a very
good
ethanol, the base precipitates 'in crystallized
on a mixture of ice and sodium chloride solution, '
and the precipitate thereby obtained is ?ltered
.35
and washed until it has become neutral. »The
'
"
.
‘
7
obtained by usingthesodium salts 'of leamino
2,4-dibromo-anthraquinone-6-
or
é7-sulphonic ’
acid or the mixture of both'isomers.
‘
Example 10
25
20 parts of a‘technical mixture containing vthe
On dilution with
form. It is then isolated by ?ltration.
15 parts of this base are dissolved in 45 parts
30
of weak oleum and heated up to 40 to 45° C., until
a test shows that it is completely soluble in
water. The sulphonation product is then poured
.
isomers sulphonated in the 5- and 8-position. 7 Similar easily water-soluble blue dyestu?s are 9
v25 quinone and 0.2,part of copper powder is heated
on a re?ux during 24 hours.
solubility.
As' starting product it is’ also possible-to use
the sodium’ salt of l-amino-Zflwdibromo-anthra
quihone-8—sulphonic vacid or the mixture of the
potassium; salts of. .leamino-é-bromo-anthra
quinone-2,5-,disulphonic acid and l-amino-4
acid, 5
' bromoaanthraquinone-2,8-disulphonic
parts .of sodium bicarbonate, 0.2, part of copper <
powder, 150 parts of water, 50 parts of ethanol
and 20 parts of l-amino—2,4,6-trimethylbenzene
are heated, on a re?ux during 24 hours and the
dyestu? thereby formedris precipitated by .an ad
dition of hydrochloric, acid. The precipitate is w Ul
moist paste is then mixed with BO-parts of an ' then ?ltered and worked up in the usual manner.
aqueous solution of potassium ‘sulphite (50%) It dyes wool blue shades of good jiastn‘ess prop
and 60 parts of phenol and heated in an auto
Example '11
clave for 16 hours at 110° C. After elimination
140 of phenol by means of distillation with water
20 parts of l-amino-2¢sulpho-4-bromo-anthra 40
steam, the solution is ?ltered and ‘the dyestuif quinone, 10 parts of sodium bi-carbonate, 0.2
salted out. The dyestuff thereby obtained pos
part of copper powder,’ 50 parts of ethanol, 20
parts of 1-amino-2,4,6-trimethylbenzene and 150
N112
parts of Water are heated together under stirring
.
|.
345
00
at 70° C. until the formation of the dyestu? has 5
erties.
sesses
the
formula:
'
'
'
.
'
.
1
'
O/ \ 40.11
occurred. Ethanol and the excess of the aromatic
base are thereupon distilled off with water steam,
and the dyestuff, which precipitates thereby in
\oo/
| 3
sonar
crystallized form, is ?ltered. By dissolving .it in
5,0
Water and acidulating its‘aqueous solution with
sulphuric acid, it can be precipitated in pure
form.- It dyes wool brilliant well levelling blue
and dyes wool pure blue shades of good proper; shades of excellent fastness to washing and to
on
HN~< E;-—CH3
55 ties to washing.
,
light and possesses the formula:
By using as aromatic base the l-amino-2,4,6-,
trimethylbenzene a dyestuff possessing a pure but
a little redder shade will be obtained.
R60
7
NH,
‘
'
'
Example 9 ‘
20 parts of the sodium salt of 1-amino-2,4
dibromo-anthraquinone75~sulphonic acid, 5 parts
of sodium bicarbonate, 0.2 part of copper pow
der, 150 parts of water, 50 parts of ethanol and
5.65 20 parts of 1-amino-2,4,6-trimethylbenzene are
heated on a reflux during 20 hours.
The reac
tion mixture is then distilled with Water steam
in order to drive oil the ethanol and the excess
of the aromatic base, and the di?icultly soluble
dyestuff separated by ?ltration and washed with
salt Water.
This dyestu? still in moist state is then mixed"
7
CH3
, Example 12
'
14 parts of the dyestu? prepared according to
Example 3 from 1—methylamino-4-bromo-‘
anthraquinone ' and‘ l-amino-2,6-dimethylben
zene are dissolved in 180 parts of concentrated
sulphuric acid and precipitated by means of an 70
addition of 57 parts of water. The suspension
is then stirred ?rst for several hours at normal
with 20 parts of an agueous solution of potas
temperature, then for 2 hours at 40-60° C. with
sium sulphite and 50 parts of water and heated 7.5 parts of the crystallized sodium salt of benz
75 under pressure during 16 hours at 140° C. Af . aldehyde disulphonic acid, and the reaction mix 557.5
‘.ture“ poured
v
into 5001:; ‘partsofwatei‘.
V ,
, The pre$2,121,928,
0’
cipitate thereby‘obtained is‘?ltere‘d, suspended in
'
"
'
‘
~
'
~ Eaiampié
'
"
'
i
'
I_;' > _
'
'
7
v
'
'
,
1000 parts of watertheated to the boil and ?ltered
C_=acetyl-2,4edibromo-anthrapyridone is con
-.from' some ‘of the unreacted starting product? 'densed with 1-amino-2,6-dimethylbenzene in the
0‘
The dyestuff is thenwsalted out and isolated by‘ manner described in Example land the base 5"
?ltration.- It is soluble ‘in ‘water: with a blue '‘ thereby obtained, transformedinto the 2-sul
coloration‘and dyes wool vfro'man acidbath blue 7 ‘phonic acid derivative 'byheatingitjwith a cone 7 . > '
shades of 'good 'fa'stnessuto milling
spiration.
10,,
Its formula is: j"
"'IIIH-CHP
‘to per- I 'centrated potassium sulphite solution and phenol
.
'
‘
6H3.
for 16 hours at 140° C. .~
.I
OHa-HN'
‘
'
10,
‘
'
l
NH—-,
I
0
15" 7’
(ll-
'
on?
‘
—s0'3n
cm
>
V20;
p
,7
n . _
I
S6331
a
_
v
.
y_
I
“
‘20
4=__ parts of the dyestufi thereby obtained are’
1: dissolved in 35- parts of concentrated sulphuric‘
,25 r ' In a,n similar
,
mannerE it
,7 is possiblerto
.7
v transform
, 2 1‘
“At
j‘acid'andthe'solution
this temperature are
is‘cooled"d0vvn
slowly added 0.6
to part
—'6° of1
C.‘ 25
thef‘condensation product obtained according to
Example 4 {from I 1_--amino-2~inethyl4-bromo' anthraquinone and l-amino-2,6-dimethylbenzene
into. a ~vvater-sol11b1e violetmdyestu?giofr the
peroxide of manganese of'70%. The temperature ‘
: ‘is then allowed to .rise up to 0° C. and the reac->
" tion'rnixtu're is allowed to ‘stand overnight» at“
_.'ordinary temperature.‘ ‘The reaction mixture is: '
' _.-then heated for av short time at 40° C. and poured->130-v
‘30 _formula:. ' w
‘iN’IHI‘p
_VCOY,
/
‘
'
,.,
7
OH:
I’
i
If?“
I
7
70H:-
co‘wvl‘ifll'
‘
r
--
~j:;l_,
I‘
v
v
40
O0
/
‘
i
'
f
.
I
Q
7
we
l
a:
n
.
CF‘
.
‘
-'-so,H
a
v
‘
1
'
'f
'~
'
"'40
I ; into coldwater,v whereby’ the produced dyé'stu?
y'precipitates. The dyestuff is separatedbyy?ltra
‘
V
p I
tion, redissolved in water, neutralized 'and'salted _'
I
453
'i I
‘
- v
I
some '
Example 13
7
.-
:
‘
.y-,ij_,out_
;»' ,'The new dyestuff
,
dissolves in,
. vvater
I
g
_Vwith'blue
o
_ 0 red coloration and'dyes wool blue red tints of
n V , l0‘rparts oi‘the?condensation product obtained; good fastness to light and to milling. 'Its formula ..
according to Example 6 from 1-amino-2,4-di-.
~
‘
is:
‘
bromo-anthraquinone and 1-amino-2,6-dimethy1-;2>: 1.: ‘i
'
“
i
‘5013benzene are dissolved in 60 parts of sulphuric
'
acidv of 80%‘ and heated during 4 hours at 60° '
"
C. and under good stirring with>4.5 parts of the '
01,1?‘ _
I
-
'
'
, ._
‘
50f
"'
H '
~ sodium salt ;of benzaldehyde disulphonic acid I
o.‘ 55: poured
(cryst.)_.into
The
500 reaction‘
parts of Lmixture
jwater,v theisthe'reupon:
precipitated 1
‘
i: , dyestu? "separated by??ltration, redissolve_d__ in _ 4 ,
‘ ‘water, neutralized and salted out.
7
<
555"
The dyestu? ‘
'ther'eby
‘very good
“obtained
fastness
dyes
properties
wooliblue
and
violet
‘possesses
shadesthe
of 1;
?orformulaz
"
7
~
‘
"'
"
a
v
V‘
v
75'
I
>.
i
,
‘
:
‘J60
x
._
65"
~15
,
2,121,928;
’
7?
wherein X stands for a ‘memberof the group con;
'WhatIclaim‘ist.
~
1. A process forgtheof'anthraej. sisting of methyl and ethyl, .Y stands for a mem
' 1 quinone‘ dyestuffs, comprising condensing 'an-, ber of the group consisting of methyl, ethyl and '
I
thraquinone compounds containing in- an u-po
halogen, and Z stands fora member-of the group
sition at least one-member of the group consist}
consisting of hydrogenandl methyl.‘
e
'
'
5. A process forj'the;manufacture :of anthra
ing of ‘halogen, nitro, alkoxyand hydroxy with, ,
'
‘I quinone dyestuffs, comprising condensing vsul-v
an aromatic amine of the general formula
phonated ,anthraquinone compounds containing _
at least one halogen atom in an a-position withvv
'
'
an aromatic ,amineiof the general formula: ,
"10
105
11 $112
I15 wherein X standsqfora member of the'group‘c'on
> sisting‘ of methyl and, ethyl;Y_,-stands foria-mem-ij
' ber ofétheggroupconsisting of methyL'ethylland -
'
halogen, andv Z stands-lfonaimember of, the group ,
I wherein Xstands for a member of the group con
311T” consisting of, hydrogenandmethyl, , . .
sisting of methyl'andiethyl, Y stands for a mem-_ ~
21.=;A, process. for‘ = the manufacture of anthra- ‘
quinone dyestuffs‘, ‘ comprising 1 ,condensing,.,an- . ber‘of the groupiconsisting of methyl, ethylxand
.thraqui'nonecompounds.oontainingiin anv a-po- ' halogen, and Z stands ,for a member of- the‘ group
consisting of hydrogen and methyl, andiperforme :
' sitioni at‘ least.- one member of the group consist
ing of halogen, nitro, alkoxy and hydroxy;,~-in ‘ ing- the condensation in presence of a solvent‘and-w'
25 presence of a solvent and diluting agent, with an a diluting agent, of copper as catalyst and of an
~ acid-binding ‘agent atia temperature of 50° to
aromatic amine of the general formula '
'
250°
re
vC.
.
.
.
6. A process forthe manufacture .of anthra
_
quin0ne.;d'yestuffs, comprising condensing‘ an an- '
" thraquinoneaderivativeof thelgeneral formula’ . »
= 30'
301
35 wherein X stands foria?member of the group con-‘3
sisting of methyl and'e'thyI, Y stands for a mem
ber ' of the‘group-“consisting 'of'imethylfethyl and, , _
7740*
halogen, and'Z stands fori-amember of the group
consisting
v3. A" process
of hydrogen
for theima'nufacture'
and‘ methyl. of anthra - wherein representsa member of thegroup con
quinone dyestuffs, comprising condensing anthra- , sistin'g'tof‘ hydrogen, halogen,lalmino and methyl- .
quinone compounds containingin an’ a-position amino; B"re'pres_ents“halogen,"C represents'_ a '
at least one member of ‘the group consisting of , member of the group consisting of hydrogen,
. halogen, nitro, alkoxy- and hydroxy, in presence
V»
,of a solvent and’ aHdiluting agent and copper as
catalyst, with aniaromatic amine of the gen
era1+f0rmu1a>
.
> I
‘
"
I
;‘ ;.;
‘
~
~
I1
halogen,‘ alkyl and-sulpho, and D represents a‘
member of the, group-‘consisting of hydrogen;
halogen‘and a sulpho groupfwith anjaromatic; Y
"amine of the general formula.
.‘NEB
wherein-X stand'shfor-y'armember ofthe group
consisting, zofgmethyl»; and ethyl; Y , stands ‘for a
member ofthejgronp consisting,v of methyl, ethyl
andfha'loge'n,‘ and‘ Z stands for a member of the
group consisting of hydrogen and methyl. - 4 g
so -'
4. A process ‘for I the manufacture of anthra
quinone dyestuffs, ‘comprising condensing an- 7
- thraquinone compounds‘ containing‘ in an 'm-po-.
sition at least one member of the group consist
ing of halogen, nitro, alkoxy and hydroxy, in
r65
presence. of a solvent and a diluting agentyof
copper as catalyst and of an acid-binding agent,
whereinHX, ‘stands (for a member ofzthe group
1
consisting",ofvzmethyl yandfethyl, .3; stands for a, _
member birth-é group "consisting of methyl, ethyl , 4'
and halogen,‘and Z stands for a member of the 56 '
group consisting of hydrogen and methyl.
,
V
O
'7. A process for the manufacture of anthra
quinone dyestuffs, comprising‘ condensing sul
phonated anthraquinone'compounds of the gen
eral formula:
v
‘
'
0
‘
i
[65,
tire-R
' at a temperature between 50° and, 250° C.,-with.
an} aromatic amine of the general formula
70
V‘
' lfH:
II
0
halogen
I
10
wherein R represents a member of the group con-V, '
sisting of hydrogen and methyl and D represents
a member of the group consisting of hydrogen, _ 75
~
_
8
$121,928?
halogen, and-'sul‘phonio acid>group1, withJan arol : V 12. The anthraquinone dyesmirsfofl“ the ge?~
matic- amine of the general formula}
'
‘
eraliformurla:
i
10 "
and halogen, and Z stands for a member of the
15 group consisting of hydrogen and methyl and
performing the condensation in presence of a
solvent and a diluting agent, of copper as cata
lyst and of an acid-binding agent at a tempera
ture of 50° to 250° C.
V
V
'
8.'A. process for the manufacturev of‘an'jan
20
-
"
" - "
'
o=
V
I
~
'
IFH-‘R'
wherein X stands :for' a member’ of the group‘
consisting of methyl andl'ethyLVY stands for a
member of the group consisting of methyl, ethyl
'
1
thraquinone dyestuff, comprising condensing‘
l-amino-Z-sulpho'-4-bromo#anthraquinone ‘with
l-amino-Z/LG-trlmethylbenzene' ‘in presence of i
a solvent and a diluting agent, of copper as cata
lyst
and‘ of an acid-binding agent at a tempera
25
ture of 50° to 110° C.
'
'
V i _
"
9. A process for the manufacture" of an‘ anthra—
quinone dyestu?,‘ comprising condensing l-‘amii- I
10’
wherein R represents a member of the group con
sisting of hydrogen and methyl, D represents a
member of the group consisting of hydrogen,
halogen; an'df'sulpho, X represents a" member ‘ of
the groupconsistingof methyl: and ethyL'sY rep
resents-Ia member of the'igroup“ consisting: of
methyl, ethyl; and‘ halogen,‘ Zr represents a mem
ber of , the group’ consisting of“ hydrogen’ and
methyl‘, and V represents’ a member‘ of the‘ group
consisting of hydrogen and sulpho,'said' dyestu?s
being in: dry.‘ ‘state: dark‘ powders‘, soluble in‘ water
with blue‘doloratibri! and? dyeing" animal ?bres
blue
shades.‘
'
.
’
v
I
'
..
i
'
'.
‘13. The anthra'q'uinone dyestuff of the 'for
mula:
'‘
"
'
no-2-sulpho-4¢bromo-anthraquinone' with' I'
30'
amino-2,6-dimethylbenzene V in presence‘ of ' a‘ so-l- '
‘vent and a diluting'agent, of copper vas'a catalyst. "
3053
and'of an acid-binding agent at a temperature of
50° to 110° C.
.
~
‘'
>
10. A process for the manufacturerof an an-'
35
thraquinone dyestu?, comprising vcondensing
1—amino-2-sulpho~‘l-bromo-anthraquinone With
1-amino-2-ethyl-4,6-dimethylbenzene Vin pres
ence of a solvent and‘ a diluting agent, of copper '
as a catalyst and of an acid-bindingv agent at a
l4. 'Iheanthraoujnone dyestufflof' theiiormula i; ’
NHs.
'
temperature of 50° to 110°C.
11. The anthraquin'one dyestu?s containing‘ini' ’
an u-p‘osition at least once in their molecule the '
grouping
e
r '
X
7
~.
7V7
r 4,5;
Z
15. The anthraquinoneidyestu? of the-‘formula?
wherein X stands for a member of the’ group
50 1
consisting of methyl and‘ethyl, Y stands for a
' member of the group‘ consisting of methyl, ethyl
and halogen, Z stands for a member of the group
consisting} of hydrogen and'methyl, and V repre
sents a member of the group consisting of hydro
and' sulpho, said dyestuffs being valuable
551. gen
compounds for dyeing lacquers and cellulose
esters and ethers and in case they are soluble in
water being suitable fordyeinganimalg?bres. "
' g
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