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Патент USA US3035068

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United States Patent 0. "ice
3,035,053
Patented May > 15., 1 962
2
1
wherein A, R, R1, ‘X, Y and n possess the aforeci'ted
meanings and wherein the group
3,035,058
DYESTUFFS OF THE ANTHRAQUINONE SERIES
CONTAINING DECHLOROi’YRE/IIDYL
A
Jacques Guenthard, Basel, Switzerland, assignor to
Sandoz Ltd, Basel, Switzerland
No Drawing. Fiied Nov. 25, 1958, Ser. No. 776,197
Claims priority, application Switzerland Nov. 29, 1957
6 Claims. (Cl. 260—256.5)
—N
\
H
is in para-position to the —NH— group, with at least
1 mole of a cyclic, six-membered diazine compound con
taining three or four halogen atoms combined with car
This invention relates to dyestuffs of the anthraquinone 10 bon atoms.
The dyestu?s of Formula II which are used as start
ing substances are either l-aminoanthraquinone.deriva
the formula:
tives or 3-azabenzanthrone derivatives. Particularly in
series which contain reactive groups and correspond to
tercsting representatives of the l-aminoanthraquinone
compounds are, i.e. l-amino-2-(4’-methyl)-, -(4'-ethyl)-.,
-(4'-tert.hutyl)-, -(4'-tert.amyl)- or -(4’-iso-octyl)-phen
oXy-4—(4"-amino)- or -(4”—methylamino)-phenylamino
anthraquinone-Z'.2”~disulfonic acid, 1-amino-2-(S'~meth
yl)-phenoXy-4-(4”-amino) - phenylamino-anthraquinonel
2'.2"-disulfonic acid, l-amino-2-(4'-methyl)-phenoxy-4
[(4”-arnino)-phenyl]-phenylaminoanthraquinone-Z’.2"- or
Z
(I)
2’.2"’-disulfonic acid.
1
.
.
I
Of the 3-azabenzanthrone derivatives the following
may be named as examples: l-benzoyl- or l-acetyl- or
wherein
l-carbethoxy- or 1-carbomethoxy-Z-hydroxy-4-phenoxy
A stands for hydrogen or a low molecular alkyl radical, H
6- (4"—amino ) - or - (4”-methylamino ) -phenylaminc-3-aza
R for an aryl radical which may be substituted,
R1 for a phenyl radical which may be substituted,
X for oxygen and
Y for the amino or, together with X, for the grouping
benzanthrone-4'.2” di- or -2'.4’.2"-trisulfonic acid, 1-.
acetyl- or ~1-benz0yl- or 1-carbethoxy-2-hydroXy-4-(4'
or S-methyD- or -(4'-tert. butyl)- or -(4’-tert. amyl)— or
-(4’-iso-octyl)-phenoxy-6-(4"-amino)- or -(4"-methyl
amino) - phenylamino-3-azabenzanthrone-2’.2"-disulfonic
acid, l-acetyl- or l-benzoyl- or 1-carbethoxy-2-hydroxy-_
4-phenoXy-6-[4"-(4"'-amino) - phenyl]-phenylamino-3
azabenzanthrone-4'.2”- or -4’.2”'-di— or -2'.4'.2"- or
35
in which
R2 represents a low molecular carbalkoxy radical, a low
molecular alkylcarbonyl radical or a phenylcarbonyl
radical which may be substituted, and
R3 represents the hydroxy group, a low molecular alkyl
radical or a phenyl radical which may be substituted,
when R2 denotes a low molecular carbalkoxy radical,
-2'.4’.2"-trisulfonic acid, l-carbethoxy - 2 - methyl- or
-phenyl-4-phenoxy-6- (4”-amino ) - or - (4"-methylamino ) -
phenylamino-3-azabenzanthrone-4’.2"-di- or -2'.4’.2”-tri
sulfonic acid, l-carbethoxy- or l-carbomethoXy-2-methyl
or -phenyl-4-(4'-methy1)- or -(4'-ethyl)- or -(4’-tert.
(4"-amino)- or -(4"-methylamino)-phenylamino-3-aza
benzanthrone-Z'.2”~disulfonic acid, l-carbethoxy-Z-meth
yl- or -phenyl-4-(4'-methyl)-phenoxy-6-[4"-(4"’-amino)
phenyl]-phenylamino-3-azabenzanthrone-2’.2”- or 2’.2”’-‘
disulfonic acid. Trichloropyrimidine, .tribromopyrimi
or represents the hydroxy group, when R2 denotes a
idine and tetrachloropyrimidine are examples of diazine
low molecular alkylcarbonyl radical or a phenylcar 45 compounds coming within the scope of the present proc
bonyl radical which may be substituted.
Z for the radical of a cyclic, six-membered diazine com
pound containing two or three halogen atoms com
bined with carbon atoms, and
n for one of the integers 2 or 3,
and wherein the group
ess.
_
.
The reaction of the dyestuils of Formula II used as
starting substances with a cyclic, six-membered diazine
50 compound containing three or four halogen atoms com
bined with carbon atoms is carried out preferably in aque
ous medium. For this purpose the trihalogeno- or. tetra
halogeno-diazine compound may be applied as such .in
concentrated form or in solution in an organic solvent.
55 Acetone is an outstandingly suitable solvent.
'
The reaction temperature is adapted to the reactivity
of the individual starting substances and varies between
stands in the para-position to —NH-—.
The process for their production consists in reacting
1 mole of a dyestutl oi the formula
40° and 100° C. If it is desired to conduct the reaction
at temperatures above 50-60° C., it is advisable .to work
in closed vessels ?tted with re?ux condensers.
'
The reaction is effected in a weakly alkaline medium,
preferably within the pH region of 10.0 to 7.0. To neu
tralize the hydrogen halide formed an acid-binding agent
such as sodium or ammonium acetate may be added at,
Y
the start of the reaction or, alternatively, small portions
of sodium or potassium carbonate or bicarbonate in solid
powder form or as a concentrated aqueous solution may
be added during the course of the reaction. Aqueous
solutions of sodium or potassium hydroxide are also suit
able as neutralizing agents. The addition of small
amounts of a wetting or emulsifying agent to the reaction
(II)
mixture can accelerate the rate of reaction.
3,085,058
a
4
v
In the reaction of the trihalogeno- or tetrahalogeno
diazine compound with the —~NH—-A group only one
halogen atom reacts with an exchangeable hydrogen
EXAMPLE 8
38.35 parts of sodium 1-benzoyl-2-hydroxy-4-(4’
atom.
methyl) - phenoxy - 6 _ (4"-amino)-phenylamino-3-aza
On completion of condensation the dyestulf formed is
benzanthrone-Z’.2f'-disulfonate are dissolved in 1000
salted out from the previously neutralized solution or
parts of water at 60°. ‘10 parts of trichloropyrimidine
suspension with sodium or potassium chloride or precipi
are added, the temperature increased to 80°‘and a pH
tated with an acid. It is then ?ltered with suction,
value of between 8.0 and 9.0 is maintained by addition
Washed neutral, and dried.
The dyestuffs obtained in accordance with the present 10 of a 10% sodium carbonate solution. The mass is
stirred until such time as the starting substance is no
process are suitable for dyeing, padding and printing
longer indicated in a sample by chromatography on a
?bers of vegetable and animal origin, ?bers of regener
talc column.
ated cellulose, casein ?bers, animalized cellulosic ?bers,
The dyestuffs is precipitated by means of 100 parts of
polyamide ?bers, mixtures of the preceding ?bers, and
leather. The dyed material is treated in the dyebath or 15 common salt, ?ltered off and dried in vacuo.
100 parts of a cotton sateen fabric are padded at
room temperature with a 2% aqueous neutral solution
in a subsequent operation with an agent of alkaline re
action with heating. The dyeings possess good fastness
of the above dyestuif in presence of l gramvper liter of
turkey red oil, and ‘squeezed to 1.6 to 2.2 times its origi
nal dry weight. The moist fabric is treated in a developing
bath (liquor ratio 50: 1) containing 300 grams per liter of
to light, washing, milling and perspiration. Polyester
?bers, secondary cellulose acetate and cellulose triacetate
are reserved.
In the following examples the parts and percentages
common salt and 5 ml. per liter of sodium hydroxide solu
are by Weight and the temperatures are in degrees centi
grade.
EXAMPLE 1
66.5 parts of the dyestuif 1-amino-2-(4'-tert.amyl)
phenoxy - 4 - (4"-methylamino)-phenylaminoanthraqui
none-2'.2"-disulfonic acid are dissolved in 1000 parts of
water with about 25 parts of a 30% sodium hydroxyde
solution to give a neutral reaction. After the addition 30
tion of 66° Tw. (36° Bé.) for 20-30 minutes at 90—95°.
It is then thoroughly rinsed in cold water, s'oaped at the
boil for 20 minutes with 5 grams per liter of soap and
2 grams per liter of sodium bicarbonate (liquor ratio
20:1), again Well rinsed, and dried. A violet dyeing
fast to light and wet treatments is obtained.
EXAMPLE 9
of 20 parts of trichloropyrimidine the temperature is in
creased to 80° with vigorous agitation. The pH value
33.75 parts of l-carbethoxy-2-methyl-4-phenoxy-6
is maintained between 8.0 and 9.0 by the addition of a
10% sodium carbonate solution.
(4"-amino)-phenylamino-3-azabenzanthrone - 4’.2" - di
parts of sodium chloride are strewn into the solution,
sulfonic acid are dissolved in 1000 parts of water and 14
parts of a 30% sodium hydroxide solution at 60". At
upon which the new dyestu? is precipitated. 'It is ?l
the same temperature 25 parts of tetrachloro-pyrimidine
tered off, washed with a dilute aqueous solution of sodi
um chloride, and dried in vacuo at 50-60". The dark
are added in small portions and simultaneously a 10%
sodium carbonate solution is added dropwise to the solu
40 tion to maintain the pH value of 8.0 to 9.0. The tem
When the condensation reaction has run its course 100
powder obtained dissolves in water to give violet solu
tions.
perature is then increased to 80°.
solution of this dyestutf and heat-treating the padding
in presence of an agent of alkaline reaction, a bluish
violet dyeing fast to light and wet treatments is obtained.
Table 1 below lists further dyestuffs containing re—
active groups which can be produced by the process de
scribed in Example 1. These dyestuffs have the formula
? re
The reaction is com—
pleted when the starting substance is no longer indicated
in a sample. The dyestuff is precipitated with 100 parts
of sodium chloride, ?ltered off, washed with brine until
On padding a cellulosic ?ber fabric with an aqueous
neutral reaction, and ?nally dried in vacuo at 50-60".
A powder is obtained which is soluble in water with an
orange-red coloration and dyes natural and regenerated
cellulosic ?bers from weakly alkaline dyebaths in
orange-red shades which are fast to light and wet treat
50
O-Rl
ments.
In Table 2 are listed a number of dyestuffs contain
ing reactive groups Which are obtainable according to
the processes of Examples 8 and 9. They correspond
ll
0
to the formula
55
NET-R4
.To simplify the nomenclature the abbreviations DDZ
and TDZ respectively are used for the dichloropyrimidyl
radical and the trichloro pyrimidyl radical.
Table 1
Example
R1
R4
60
Shade of _
Dyeing 011
Cotton
2 _______ -_ 2’.4’edisulfophenoxy___ 4”-[4”’-DDZ~amino-
pheny]]-2”-su1fo-
blue
violet.
phenylamino.
3 _______ _.
4’-t.butyl-2’-sulto-
4"-DDZ-amino-2"-
4 _______ .-
4’-methy1-2’-sulfo-
4"-TDZ-n1ethyl
phenoxy.
phenoxy.
.
sulfophenylamino.
,
amino-2”-su1fophen
violet.
Do.
ylamino.
5 _______ __
4'-sulfophenoxy _____ __
4"-DDZ-methy1arni-
no-2”-suliopheny1
Do.
amino.
6 _______ _-
'
7-; _____ _.
4’-iso-octyl-2’-sulfo-
phenoxy.
Do.
sulfophenylamino.
4’~ethyl-2’-sulfophenoxy.
4”-DDZ-amino-2”-
"
_____do _______________ -_
Do.
70
and are characterized by the symbols R1, R2, R3 and R4
and by the shade of the dyeings on cotton.
To simplify the nomenclature the abreviations DDZ
and TDZ respectively are usedefo'r the dichloropyrimidyl
75 radical and the trichloropyrimidal radical.
3,035,058
Table 2
Example
R;
R1
R1
R1
Shade of Dye
ing on Cotton
10 _______ _. hydroxy__ acetyl _____ _.‘__ 4’-1soctyl-2’-sul1'ophenoxy_-4.__ 4”-DDZ-amtno-2"-sulfophenylamlno
violetish red.
11 ____________ __do_____ carbethoxy____ 4’-methyl-2’-sultophenoxy.--._ 4”-DDZ-(N-methy1)-anim0-2”-sul12 ____________ __do___._
benzoyl _____ _.
2C4 disulfophenoxy _________ ._
13 ____________ __do ________ _-d0 ....... -_
4'-t.amyl-2'-su1iophenoxy ____ _.
fophenylamlno.
4”[(4’”-DDZ-amino)-phenyl]-2”-sultophenylamlno
’-DDZ-am1n0-2”-su1fophenylamino__
Do.
reddish violet.
violetish red.
14 ____________ >_do.,__- carbethoxyun ._-__d0 ______________________ __ 4”-TDZ-(N-methyl)-amino-2”-su115 _______ _-
methyl__.- _...-d0 _______ .‘ 4’-methly-2’-sulfophenoxy___._
Do.
fophenylamino.
’-DDZ-(N-methyl)-amino-2”-sultophenylamino.
orange red.
Do.
16 ____________ -_do ________ "do _______ __
4Ms00ctyl-2'sulf0phenoxy._-._
4”-DDZ-amino-2"-sulfophenylamine
17 _______ __
pheny _-._ l____do _______ _-
2’,4’-dlsuliophenoxy _________ _.
4"DDZ-(N-methyl)-amino-2”-sul-
18 _______ __
methy1____
4'-t.amyl-2’-suliophenoxy ____ _.
carbomethoxy
Do.
tophenylamino.
4"-[4’”-DDZ-aminopheny1]-2”-sultophenylamlno.
red.
. 4’-n-heptyl-2’-sulfophenoxy____
Do.
4’-n-hexyl-2’-sy1tophenoxy- . _ _ _
in
D0.
phenylamino.
4'-tertomyl-T-sulfophenoxm.- _____do _______________________________ __
4’-lsopropyl-2'-sulfophenoxy___ 4”-TDZ-amino-2"-suliophenylamlno.
Formulae of representative dyestuffs of the foregoing
Do.
D0.
Example 11-
examples are:
Example l—
OH
O
i]
NH:
30:11
i
5
—O
_
0
NH
a! \
N
CtHu tart.
SOzH
ll
HaCz-‘OOC-
'
CH;
30511
O
10
CH,
‘ SOgH
/
—N
0H.
|
\
0
NH
—N
DDZ
DDZ=radical of dichloropyrimidine
/
\
DDZ
15
Exam le 24
Exarnple 3-
p
O
l
NH?
$03K
l
|
7
—~O—C>~C4Hw tert.
ll
EH
20
O-co-
N
SOzH
soan
0
0 NH-O-NH-DHZ
25
*OaHu. WM.
SIOZH
Example 8—-—
|
I
NH-~
CH
l
—N\
‘,H
DDZ
C
30
CO"?/ ‘Y
50 H
I '
Having thus disclosed the invention what I claim is:
1. An anthraquinone dyestuff of the formula
0
CH1
SO|H
ii
0
35
A
i
i ’
NIL-ONH-DDZ
Exam p1e 9——
\N R D 80 H
_ _ _( ’ )“
Z/
.
40 wherein
e"
c
A is a member selected from the group consisting of
H5Ca__OOC_(/( \N
I
hydrogen and lower alkyl;
l
45 R is a member selected from the group consisting of
O_C>_SO:H
phenylene and biphenylene,
Z is a member selected from the group consisting of
S031;
dichloropyrimidyl and trichloropyrimidyl, wherein the
l
chlorine atoms and the group —-NA-- are each bound
H
\
0
NH—C>—NH_DDZ
50
to a carbon atom of the pyrimidine ring;
n is an integer ranging from 2 to 3; and
3,035,058
7
8
D is a member selected from the group consisting of
2. The anthraquinone dyestuf‘r' of the formula
NH;
c v.
9
NH,
503E
v
wo “Bl
C‘)
SOaH
CH3
NH
dichloropyrimidyl
10
3. The anthraquinone dyestutf of the formula
OH
NH;
80:11
15
SOIH
NH-r
20
~NH-dichloropyrimidyl
4. The anthraquinone d-yestulf of the formula
\
Goo-6l \N
25
.
80:11
0;
—CH;
503B
30
NH
—NH-dlchloropyrlmidyl
5. The anthraquinone dyestuff of the formula
v
35
(‘)H
6 s
HsCn-OOC—-l
N
SIOIH
SOiH
‘0
CH:
/
NH—
N
\
.
45
.
.
diehloropyrimldyl
6. The anthraquinone dyestu? of the formula
wherein
C
R1 is a member selected from the group consisting of
phenyl and alkylphenyl wherein alkyl has from 1 to 8 50
carbon atoms;
R2 is a member selected from the group consisting of
Q
l‘
69*‘
O—-®—CsHn-tertiary
SOgH
carbomethoxy and carboethoxy;
R’;, is a member selected from the group consisting of
acetyl and benzoyl, and
_
NH-
55*
N
\
dichloropyrimidyl
R3 is a member selected from the group consisting of
methyl and phenyl;
the group —NH-- in D standing in para~position to the
60
group
References Cited in the ?le of this patent
UNITED STATES PATENTS
Peter et al ____________ __ Dec. 25,
2,580,190
2,759,940
1951
Bucheler et al _________ __ Aug. 21, 1956
2,773,871,
Brassel etal ___________ __ Dec. 11, 1956
FOREIGN PATENTS
65
349,126
Great Britain ________ __ May 19, 1931
a '1
‘
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3,035,058
May 15L. 1962
Jacques Guenthard
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
Column ll lines 54 to 57, the formula should appear as
shown below instead of as in the patent:
A
/
—N
column 3, line 29, for "hydroxyde" read —— hydroxide —--;
column 4, lines 57 to 66, lower right-hand portion of the formula‘J
for
I
NH-R
read
l
NIT-R4
column 5, lines 19 to 25, lower right-hand portion of the
formula,
for "—NH-DHZ" read -— -NH—DDZ ——.
Signed and sealed this 20th day of November 1962.
(SEAL)
Attest:
ERNEST W. SWIDER
DAVID L. LADD
Attesting Officer
Commissioner of Patents
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