close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3074935

код для вставки
3
United rates Patent i9 "ice
3,674,925
Patented Jan. 22, 1953
2
1:
3,074,925
AZO ANTHRAQUINONE DYESTUFFS CON
TAINING A TRIAZINE
Robert Norman Heslop, Blackley, Manchester, England,
assignor to Imperial Chemical Industries Limited, Lon
don, England, a corporation of Great Britain
No Drawing. Filed June 4, 1959, Ser. No. 817,981
Claims priority, application Great Britain Nov. 29, 1954
6 Claims. (Cl. 260-153)
10
This application is a continuation-in-part of application
Serial No. 549,176, ?led in the United States Patent Of?ce
on November 25, 1955; and of application Serial No.
732,841, ?led May 8, 1958, as a continuation-in-part of
application Serial No. 549,160, ?led November 25, 1955,
now abandoned, which application Serial No. 732,841, is
and
l
which radicals contain at least one strongly acid solu
bilising group. The benzene nuclei in A may also contain
now United States Patent 2,892,670, having issued June
other substituents, especially chlorine atoms, lower alkyl
30, 1959.
groups or lower alkoxy groups, e.g. methyl, methoxy
The present invention is concerned with water-soluble
dyestuifs of the triazine series. More particularly the 20 and ethoxy groups, without markedly affecting the gen
eral properties of the dyestuils.
invention is concerned with water-soluble dyestu?s of the
The new dyestutfs may be obtained by the condensa
tion of cyanuric chloride with about one molecular pro
triazine series which contain both an azo chromophore
and an anthraquinone chromophore.
It is well-known, for example, from British Patents
portion of an amino-azoanthraquinone compound which
Nos. 466,886 and 554,463, that water-soluble dyestu?fs 25 is represented in the acid form by the formula:
of the triazine series may be obtained which contain both
an azo chromophore and an anthraquinone chrornophore.
In the dyestuffs hitherto described, this has been achieved
by condensing an m-aminoanthraquinone compound
which contains a reactive amino group and an amino-azo
dyestuff containing a reactive amino group with a cyanuric
halide, and usually replacing the ?nal halogen atom of
0
II
run
I
-—SOaH
30
(503.11)“
(I)
NH-A-NH:
the cyanuric halide by reaction with an amine, e.g. aniline.
in which A and n have the meanings given above. The
We have now found that valuable dyestu?s may be
said aminoazo anthraquinone compounds used in this
35
obtained by condensing cyanuric chloride with certain
manner are mainly novel but may be obtained by general
water-soluble amino compounds which contain both the
methods in themselves known from the past, for ex
mthraquinone and the azo chromophore in such manner
ample, by condensing a diaminoazobenzene which con
that two chlorine atoms are left attached to the carbon
tains a strongly acid water-solubilising group with a 4
atoms of the triazine ring. The dyestuffs forming the
bromo-l-amino-anthraquinone-Z-sulphonic acid or a 5-,
subject of the invention may be broadly represented, in 40 6-, 7- or 8-sulphonic acid derivative thereof, or by cou
the acid form, by the formula:
pling a diazotised aniline containing a strongly acid
water-solubilising group with a l-amino-4-(m-amino
anilino)anthraquinone-Z-sulphonic acid or a 5-, 6-, 7- or
S-sulphonated derivative thereof analogously to the
method described in German Patent No. 659,591.
The reaction of the said aminoanthraquinone com
pound with cyanuric chloride is preferably carried out in
aqueous medium at a low temperature, preferably be
50 tween 0 and 10° C. Advantageously the reaction medium
is maintained at or about neutrality by the addition of
acid-binding agents such as sodium carbonate during the
reaction so as to neutralise the hydrochloric acid formed.
the azobenzene series which contains at least one strongly
If desired, an excess of cyanuric chloride may be used
acid water-solubilising group, for example, a sulphonic
to
allow for hydrolysis.
55
acid group or a carboxylic acid group. In general A will
The new dyestuffs so obtained can be isolated from
not contain more than two such groups.
the medium in which they are produced by the commonly
The dyestuffs so de?ned have a similarity of dyeing
used methods, for example by salting out the dyestuti in
properties as‘hereinafter set out which are determined
the alkali-metal salt form and ?ltration or by spray
by these broad structural features and which are little
the whole reaction mixture. Owing to the pres
a?ected by the variations of structure possible within 60 drying
ence of the labile chlorine atoms in the molecule it is
these de?nitions, or by the presence or absence of non
desirable to carry out the drying cautiously, for example
solubilizing groups in A.
at a moderate temperature such as between 29° C. and
wherein n stands for 0 or 1 and A stands for a radical of
.Thus, the nitrogen atoms linking the azobenzene radical
A to the anthraquinone and triazine nuclei may be at
40° C. and, if desired, under reduced pressure. The ad
dition of certain buffers aids the stabilisation of these
tached to the same or diiferent benzene nuclei, so that A 65 labile chlorine atoms especially valuable being mixtures
may represent such radicals as for example:
of alkali metal hydrogen phosphates and mixtures of
the free acids and alkali metal salts of dialkylarylamine
sulphonic acids (e.g. diethylmetanilic acid) in which the
70 alkyl groups contain 2 or more carbon atoms.
The new dyestutfs are suitable for dyeing or printing
a wide variety of material, for example wool, silk and
3,074,925
3
4
polyamide materials, and are especially valuble for use
on cellulose textile materials such as linen, viscose rayon
These dyestuffs have the formulae:
O
and cotton when dyed in the presence of an a kali or when
NH:
H
the dyed material is after-treated with an alkali. On these
|
S0311
materials they give olive-green shades which are very 6
fast to washing and to light. They are especially suit
able for dyeing cellulose at or about room temperature
in an aqueous alkaline both which contains a salt, and
may also be ?xed on cellulose by padding or textile print
ing methods incorporating a treatment with an alkali, 10
and if desired, a short heat treatment.
,
ferred those in which A represents a radical of the
/C\
‘It
H038 c“) 11IH®N=N~©~NH~o \ % 0-01
A 0:13:
N
and
The preferred dyestuffs of the invention are those in
which A of the general formula represents a 4:4’-radical
of the azobenzene series containing a sulphonic acid
group or a carboxylic acid group, and above all are pre
(In
O
NH:
H
I
S0311
15
Z1
formula:
/ \
.
20
If ‘I
Hot 0 liIHON=N—
ml.\ % $-01
SOaH
N
02H
wherein A1 stands for a ‘1:4-monocyclic radical of the
benzene series.
The invention is illustrated but not limited by the
‘following examples in which parts are by weight:
respectively.
In place of the trisodium salt of 1-amino~4-[4'-(4"
amino) phenylazo] anilinoanthraquinone - 2:2":5 - trisul
25 phonic acid used in the above example there is used an
equal weight of 1-amino‘4-[4'-(4”-amino)phenylazo]
anilinoanthraquinone-2z2”:S-trisulphonic acid, a dyestuif
Example 1
A solution of 4.06 parts of cyanuric chloride in 20
parts of acetone is added gradually to a stirred mixture 30
of 50 parts of water and 100 parts of crushed ice. To
the stirred suspension of cyanuric chloride thus obtained
there is added at 0° to 4° C. during 1 hour a solution
in 250 parts of water of 14.8 parts of the trisodium salt
of 1-amino-4-[4’-(4"-aminophenylazo)~aniline]-anthra 35
quinone-ZzZ":S-trisulphonic acid, which may be prepared
of the formula:
11038
g‘)
NH:
S0111
01
\
I
I
0
NH
N/ \III
N=N
NH-ii
0-01
%
by condensing 4-bromo_l-aminoanthraquinone-Z:5-disul~
SOaH
phonic acid with 4:4'-diamiuoazobenzene-2-sulphonic acid
is obtained. It dyes in shades slightly bluer than the
in alkaline medium. The mixture is stirred for a further
40 minutes at 0°—4° C. and then sufficient 2 N sodium 40 dyestutfs of the formulae indicated above.
carbonate solution is added gradually during 30 minutes
Example 2
A solution of 0.93 part of cyanuric chloride in 16 parts
of acetone is added gradually to 100 parts of water stirred
at 0° to 2° C. To the stirred suspension of cyanuric chlo—
to render the reaction mixture neutral to litmus. A solu
tion of 11.4 parts of disodium hydrogen phosphate and
7.2 parts of potassium dihydrogen phosphate in 100 parts
of water is added, the mixture is stirred for 10 minutes
and then su?icient sodium chloride to give a concentra 45 ride so obtained a solution of 3.37 parts of 1-amino-4~(3'
amino - 4’ - phenylazo)anilinoanthraquinone - 2:2”:5”
tion of 50 grams per litre is added and the mixture is
stirred for 3 hours when separation of the dyestuff is com
plete. The mixture is ?ltered, and the solid on the ?lter
is washed with a solution of 25 parts of sodium chloride,
11.4 parts of disodium hydrogen phosphate and 7.2 parts 50
of potassium dihydrogen phosphate in 500 parts of water,
and ?nally dried at atmospheric temperature. The prod
not so obtained has the formula:
0
H
NH:
l
-SOaH
maintained at 5° to 10° C. and the pH at between 5.5 and
6.5 by the addition of 2 N sodium carbonate solution.
After stirring for one hour longer, a mixture of 0.5 part
of disodium hydrogen phosphate and 1.0 part of potassium
dihydrogen phosphate is added. When these have dis
solved, the reaction mixture is ?ltered, sodium chloride is
55 added to the ?ltrates and the dyestuli so precipitated is
?ltered and washed on the ?lter with a solution of 40 parts
or
N
trisulphonic acid in 200 parts of water is added during
about 1 hour the temperature of the reaction mixture being
/C\N
5.
of sodium chloride, 1.35 parts of disodium hydrogen phos
phate and 2.7 parts of potassium dihydrogen phosphate in
200 parts of water and ?nally dried at room-temperature.
60 The dyestuli so obtained has the formula:
i’ re
SOZH
which yields olive-green shades on cotton and viscose.
By replacing the above trisodium salt of Lamina-4 65
[4'-(4"-amino)phenylazo] anilinoanthraquinone - 2:2":5
.
trisulphonic acid with equal parts of the trisodium salt
of
l-amino - 4 - [4'-(4"-amino)phenylazo]anilinoanthra
quinone-Z13":5-trisulphonic acid, a dyestuft‘ almost iden
tical in shade and properties is obtained. Also by sub 70
stituting the above trisodium sulphonate with 14.1 parts
of the trisodium salt of l-amino-4-[4’-(4"-amino-3"
carboxy) phenylazo] anilinoauthraquinone-Z:5‘disulphonic
acid a dyestuff very similar in shade and properties is
obtained.
75
as
('i NH~QN=N
1%IH
0
80311
3,074,925
6
5
2:2":5-trisulphonic acid used in the above example, a
It possesses very good solubility in water and yields fast
olive-green shades on cotton, bluer than the dyestu?s of
similar dyestuif having the formula:
Example 1.
0
Example 3
5
sonar
A solution of 1.94 parts of cyanuric chloride in 20 parts
of acetone is added gradually to 80 parts of water stirred
at 0° to 2° C. To the stirred suspension of cyanuric
chloride so obtained a solution of 7.53 parts of the tri
sodium salt of 1-amino-4-[4’-(4"-aminophenylazo)-3'~
NH,
I
or
L
01
I
11“ \Ir'
10 H038 ii rim-
methyl]anilinoanthraquinone-Z:2":5-trisu1phonic acid in
/
CH3
N=NONH-o \ / b-ol
a
1
N
“$03K
200 parts of water is added during 30 minutes the tem
is obtained.
perature of the reaction mixture being maintained at less
1
What I claim is:
than 5 ° C. and the pH between 5 and 6 by the addition of
l. The dyestuffs represented, in the acid form, by the
2 N sodium carbonate solution. After stirring for 30 5
formula:
minutes longer, sodium chloride is added and the dyestu?
0
Nm
so precipitated is ?ltered off, washed on the ?lter with a
II
solution of 4 parts of sodium chloride, 1.5 parts of disodi
um hydrogen phosphate and 3 parts of potassium dihydro 20
30:11
gen phosphate in 200 parts of water and ?nally dried at
room temperature. The dyestu? so obtained has the
formula:
0
II
\
. NH--A——NH-C
.
t/ \“JC-Cl
0
0
%
N
1
(51
wherein n is 1 and A represents an azobenzene radical
which contains from 1 to 2 strongly acid water-solubilising
groups selected from the class consisting of sulfonic acid
and carboxylic acid groups, the other substituents on the
\
1103s
C
25
N112
son:
. H
t/ ‘t
N=N-®C
0-01
\N_%
CH:
NH
It has good solubility in water and yields fast olive green
carbon atoms of A being selected from the group con
sisting of hydrogen, chlorine, lower alkyl and lower
alkoxy.
35
2. The dyestuif of the formula:
t ‘is
shades on cotton.
$01K
Example 4
A solution of 1.95 parts of cyanuric chloride in 20
parts of acetone is added gradually to 80 parts of water at
0° to 2° C. To the stirred suspension of cyanuric chlo
‘°
.
.l
noas
0
('21
/O\
t‘ \t'
NH—C>N=N
ride so obtained a solution of 7.83 parts of the trisodium
30 minutes, the temperature of the reaction mixture being
$02K
(in
50
‘K
n
o
um chloride, 1.5 parts of disodium hydrogen phosphate
and 3 parts of potassium dihydrogen phosphate in 200
It ‘.1C-Cl
—NI-I-G
NH-C>—N:N—
\ 4
N
parts of water and is ?nally dried at room temperature.
55
The dyestuti so obtained has the formula:
30311
4. The dyestuif of the formula:
0
II
NH:
NE:
50:13:
30:31
a.
3. The dyestul’f of the formula:
off washed on the ?lter with a solution of 4 parts of sodi
N
NH-C \ v% C-Cl
H0313 (l) IIIH:
200 parts of water and 30 parts of acetone is added during
maintained at from 5° to 10° C. and the pH at between
S and 6. After stirring for 30 minutes longer sodium
chloride is added and the dyestu? so precipitated is ?ltered
,
$0311
salt of 1-amino~4-[4'-(4”-aminophenylazo)-5'-methyl-2' 45
methoxy] anilinoanthraquinone-Z : 2" : S-trisulphonic acid in
0
([11
(30311)“
01
('31
C
Hoag
|
5. The dyestutf of the formula:
0 CH3
(|) NH:
It posssesses good solubility in water and yields fast
SOaH
olive green shades on cotton.
70
By substituting 8.04 parts of the trisodium salt of 1
(I,
amino - 4 — [5' - chloro _ 2' - methoxy - 4’ - (4" - amino)
phenylazo]anilinoanthraquinone-Z:2":5-trisulphonic acid
Hols
for the trisodium salt of 1-amino-4-[4’-(4"-aminophenyl
azo) - 5’ - methyl - 2' - methoxy]anilinoanthraquinone
75
Cl
l
0
on
\
| ‘
NH-
N/ \N
Nn-d
(‘J-Cl
N=N
0cm
dour
N/
3,074,925
6, Thedyesm? of the formula:
0
'
NH,
'
References Cited in the ?le of this patent
'
UNITED STATES PATENTS
'
50811
C1
('31
HOalS 3 NH
cmo
5
Haller et a1 ____________ __ Nov. 8, 1932'
2,108,126
Honold et a1 __________ .._ Feb. 15, 1938
'
2,145,954
Semple et a1 ____________ __ Feb. 7, 1939
N% \N
2,892,670
Alsberg et a1 __________ .__ June 30, 1959
MMGNHJ,
403E
_
1,886,480
11,,
§N/
OTHER REFERENCES
1
Sommer: “American Dyestuff Reporter," v01. 47, No.
1° 25, Dec. 15, 1958, pp. 895-899.
Документ
Категория
Без категории
Просмотров
0
Размер файла
434 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа