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Patented Dec. 17, 1946
2,412,790
\ a ‘1 UNITED s'r
TEs PATENT OFFICE
2,412,790
nynsrnrrs OF
ANTHRAQUINONE
snares AND A THE
PaocEssoF MAKING
SAME
Samuel von Allmen and Hans Eggenberger, Basel,
' Switzerland, assignors to Sandoz Ltd., Fribourg,
Switzerland '
No Drawing! Applicatio11 Jane 20,‘ 1944, Serial
N0. 541,283. In Swi
tzeriand‘ uly 16, 1943
'
7 Claims.
1
(Cl. 260—372)
2
The present invention relates to new dyestuffs
of the anthraquinone series possessing an im
proved stability to arti?cial light and to a proc—
or organic solvent or in a mixture thereof at tem
ess for their preparation.
peratures between 50° and 150° 0., a l-amino
dyestu?s consists in condensing, in an aqueous
2:4-dihalogenanthraquinone-6- or ~7-sulphonlc
It is known that the dyestu?s of the anthra
quinone series containing in their molecule the
radical of an aromatic amine corresponding to
the general formula.
' acid with a meta-substituted aniline correspond
ing to the general formula
NH2
10
4:
~hal.
wherein X stands for a substituent selected from
wherein hal. stands for bromine‘ or chlorine, 15 the group consisting of halogen, COOH, alkyl,
R, R
possess a much redder shade than the correspond— .
ing isomers containing the halogen in p-position
to the amino group. The m-substituted com
pounds are known as being valuable violet acid
tained with sulphites in order to substitute the
20, halogen
atom by a sulphonic acid group.
dyestuifs (of. U. S. Patent No. 1,898,861,
Exam
‘
ple 6).
It is further known that the dyestuffs of the
group corresponding to the general formula
X
(I?
NH:
0
‘
>
/
.
H
2:6- or -2:7-disulphonic acid with a meta-substi
25 tuted aniline under the above-described con
densation conditions.
.—SO@H
toluidine, meta-chloraniline,
meta-bromaniline,
acid,
30 meta - aminobenzoic
H
I
meta - ethy1aniline,~
meta-aminobenzoic acid methyl ester, meta
aminophenol, meta-anisidine.
,
ha].
.
7
. “As amines used for the manufacture of the
new dyestu?s may be cited for instance meta
if
.
The same dyestuffs-1 can also be prepared by
condensing l-amino - 4 - halogenanthraquinone
‘ As sulphonated aminohalogenanthraquinones
wherein one of the X represents a. sulphonic' . which
can be used,
come into consideration, for
acid group, the other X being hydrogen, give red
example,_ 1 - amino-2z4-dibromanthraquinone-6~
dish-blue shades which change to red in arti 35
or -7-sulph0nic acid, 1-amino-2:4-dichloranthra
?cial light (of. U. vS. Patent No. 1,898,861, Ex
ample 6) .
6- or -7-sulphonic acid, 1-amino-4-bromanthra
quinone-2:6- or -2:7-disulphonic acids, l-amino
It has now been found that the dyestuffs cor
. 4 - chloranthraquinone-Zz?
responding to the general formula,
0
~
Y
or 2:7 - disulphom'c
acids, or mixtures of the‘isomers.
~The present invention will now be illustrated,
NHz
but not limited by the following examples, where
‘t
in the parts are by weight.
—s0n1
345
. (Ii tNQ‘
‘
Example 1
A mixture consisting of :
,
Potassium salt of 1-amino-2:4-dibroman
Parts
‘*thraquinone-G-sulphonic acid___'_ _____ __
10
wherein one of the Y/stands for a sulphonic
Meta-toluidine _________________________ -_‘_ 3.2
acid group, the other Y being hydrogen and 50 Sodium bicarbonate _____________________ __ 4.8
wherein X stands for a substituent selected from
Copper powder ____________ _‘_ ___________ __ 0.2
the group consisting of halogen, COOH, alkyl,
Water _________ __; ____________ _'_ _______ __
50
COO , OH, OR,‘R meaning an alkyl group, pos
Ethanol ________________________________ __ 15
sess unexpected “fastness to arti?cial light, so 55
are heated under stirring during 12 hours at 80°
that thesame are very suitable for vdyeing and
printing animal ?bres.
..
. ‘During the interaction the shade of the
reaction mass changes from red to blue. After‘
vThe‘ process for the manufacture of these. new.
- the condensation the
monosulphonated dyestuff.
9,412,790
To this solution are added 13 parts of the sd~ ‘
is separated and heated with a solution of a
sulphite, until the halogen atom has been. re-_
placed by a sulphonic acid group. The disulq
dium. salt of , 1,—amino-4rchloranthraquinone-2 :6
disulphonic acid and 0.2: part of: copper; powder,
and the mixture is heated under stirring at 80°
C., until the condensation has ?nished.
The new dyestuff thus obtained dyes animal
?bres in blue-reddish shades, which remain un
phonated dyestuff is then isolated in the usual
way.
The new dyestnfi dyes wool, silk, hairs, leather
and synthetical ?bres, like nylon, in‘ beautiful
changedl‘in' arti?cial light.
blue shades which do not change in arti?cial
~
Example 6
light.
'
The new dyestufi can also be prepared by; 10
By starting from}; parts of meta-aminobenzoic
condensing l-aminoA—bromanthraquinone¢2‘:6
acid methylester: and 15 parts of the sodium salt
disulphonic acid with meta-toluidine. Its
isomeric compound containing the sulphonic acid
of l-amino - 4 - brcmanthraquinone - 2:7 - disul
phonic acid and: working up as described in Ex
ample 3; a new dyestu? dyeing animal ?bres in
groups in 2:7-positlons has a similar shade.
pure-blue; shades, which remain unchanged in
artificial light, will be obtained.
The same dyestuil can also be prepared by
starting from 1-amino-4-chloranthraquinone
2 : 6- or -2 : fl-disulphonic acids.
.
Whatwe claim is:
, '
'
_
11. They new dyestuffs of the. anthraquinonese
Example 2
ries of the generalformula ’
A. mixture consisting of:
-
NHgii
.
_
Parts.
Potassium salt of. 1-am-ino-2z‘l-dibromam
thraquinone-‘l-sulphonic acid‘_______.____,_ 10}
.
Meta-chloraniline ______ __ _______ __' _____ __
3.9
Sodium bicarbonate _____________________ __ 4.8
Copper powder ________ _, _______________ .__
0.2
Water ________ __p _____ ____..__ ____________ __
60
Ethanol ____________ __N__________________ __
20
.
-
is heated together during 20 hours at 80° C.
After. the condensation,‘ the. monosulphonated '
dyestu?‘ is isolated , and treated. as -. described = in;
Example 1,
'
X
wherein, one Y stands for. a sulphonic acid group,
the‘ other Y being hydrogen, and wherein X
stands for a substituent, selected from: the, group .
.
The new disulphonated dyestufi dyes animal
consisting of halogen, alkyl; COOHCQOF-alKyl;
OH'and' Q-alkyL, which. dyestuffs .dye animal? and
?bres in blue-reddish shades, which remain un-:
related ?bres
changed in arti?cial. light.
changedwhen exposed to. arti?cial light‘.
Example 3‘
blue shades- which are un:
2. The new dyestu? of the-formula
NHz
- A mixture consisting of:
.
Sodium salt
of
Parts:
l-amino-ll-brornanthra
quinonep-Z : ?-disulphonic acid____'___ _.____
Meta-chloranil'ine _________ _____,_..___.__,___v.___‘_..
Sodium bicarbonate __________________ __.___... 4,8
Copper powder; _____ __._____________ __..,__V_.__
0.2’
Water ______ _'_=______ ___ ______ __ ________ __,__. :60;
Ethanol_.__. ________________ __, _______ -._ ____ ._
155
dyeing animal and related ?bres in blue shades
i'siheated for several hours at 80"» C. Therea'ction
mass is then poured into diluted- acidjand' the"
which are unchanged when exposed to arti?cial
new dyestnff separatedvv according to, theusual
methods.
light.
-
- 3. The: new dyestuffi‘of the formula}
‘
It dyes animal ?bres in-blue-reddish shades
which do not change to red, when ‘exposedto
arti?cial
light‘;
'
>
Example 4
'
H0 38
5.6 parts of meta-aminobenzoic; acidareadisa
solved at 40° C. in 6.0.partsoirwater and/neu
tralized with 3.2 parts‘of sodiummarbonatez. To;
this solution are added 10; parts of.’ potassium‘ Salt;
of l - amino r224 - dibromanthraquinone-7-sul
‘ c1’
60
phonic acid, 0.2 part of copper powder and 10
parts of water, and the mixture is heated ‘for 4
dyeing animal and related ?bres in blue-reddish
‘ shades which are unchanged when-exposed to ‘ar
hours at 80° C. and a further hour at 95° C.
After. the condensation the mono-sulphonated
ti?cial light.
I
4. The new dyestuff of‘ the formula
dyestuff is separated and. treated with a hotvsolu 65
tion of a sulphite in the manner. describedin
Example 1.
.
I
i The disulphonated dyestu? thusobtained dyes
animal ?bres in beautiful blue-reddish shades,_
B20581 -
which remain unchanged in arti?cial light.
Example 5v .
5.6 parts-of meta-aminobenzolc. acid: are. dis? ‘
solved in .801 parts :of water and neutralized-‘ widah:v
3zzip'arts. of‘i'sodium carbonate.
Hooch;
. ‘
dyeing.;-..anirna1t and»_~"rielated ?bresz'inabluezshtides ‘
2,412,790
5
6
which are unchanged when exposed to arti?cial
light.
the step of condensing the anthraqui'none coin
‘
pound of the formula
5. A process for the manufacture of new dye
0
stu?s of the anthraquinone series comprising the
step of condensing an anthraquinone derivative
of the general formula
2%
NH:
l
/
(I? NH:
H035
—SO:H
\C
0
x
\
503K
(N)
Br
with m’-aminobenzoic acidmethylester in an
x
I!
O
aqueous medium in presence of copper as catalyst
and of an acid binding agent.
halogen
'7. The process for the manufacture of a new
wherein halogen stands, for a member of the
group consisting of chlorine and bromine and
dyestu? of the anthraquinone series comprising
the step of condensing the anthraquinone com
wherein one X is a sulpho group, the other“);
pound of the formula
being hydrogen, with an amine of the general
‘
formula
20
|
Y
wherein Y stands for a substituent selected from
the group consisting of halogen, alkyl and car
with m-toluidine in an aqueous medium in pres
ence of copper as catalyst and of an acid binding
boxy, esteri?ed carboxy, hydroxy and alkoxy
groups, in an aqueous medium in presence of cop
agent.
per as catalyst and of an acid binding agent.
6. The process for the manufacture of a new
SAMUEL VON ALLMEN.
HANS EGGENBERGER.
dyestu? of the anthraquinone' series comprising
30
Certi?cate of Correction
December 17, 1946
Patent No. 2,412,790
SAMUEL VON ALLMEN ET AL.
It is hereby certi?ed that errors appear in the printed speci?cation of the above
numbered patent requiring correction as follows:
Column 2, line 35, for “4-dichloranthra-” read 4-dichl0mnthraquinone-; column 4
last formula, left-hand portion thereof, for
11035-
read
H0]
and that the said Letters Patent should be read with these corrections therein that the
same may conform to the record of the case in the Patent Office.
Signed and sealed this 20th day of December, A. D. 1949.
THOMAS F. MURPHY,
{Assistant Oammz'm'oner of Patents.
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