CHROMIUM COMPLEX DYES, THEIR MANUFACTURE AND USE

COLORANTS COMPORTANT UN COMPLEXE DE CHROME

English Abstract

NOVEL CHROMIUM COMPLEX DYES, THEIR MANUFACTURE AND USE
Abstract of the Disclosure
Chromium complex of the formula
(1)
<IMG>
wherein one of the symbols Z1 and Z2 is a nitro group and the
other is hydrogen, a nitro group, a halogen atom, a methyl a
methoxy or an acylamino group, R is a phenyl radical which is
optionally substituted by halogen, low molecular alkyl or
nitro, R1 is a phenyl radical which is optionally substituted
by halogen, low molecular alkoxy, low molecular alkyl or by
nitro, one of the symbols X1, X2 and X3 is hydrogen and each
of the others is independently hydrogen, a nitro group, a
halogen atom, a methyl or a methoxy group and Me? is a cation.

Claims

CLAIMS:
1. Chromium complex of the formula
(1)
wherein one of the symbols Z1 and Z2 is a nitro group and the
other is hydrogen, a nitro group, a halogen atom, a methyl a
methoxy or an acylamino group, R is a phenyl radical which is
optionally substituted by halogen, low molecular alkyl or
nitro, R1 is a phenyl radical which is optionally substituted
by halogen, low molecular alkoxy, low molecular alkyl or by
nitro, one of the symbols X1, X2 and X3 is hydrogen and each
of the others is independently hydrogen, a nitro group, a
halogen atom, a methyl or a methoxy group and Me? is a cation.
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2. Chromium complex dyes according to claim 1, wherein
Z1 is a nitro group and Z2 is a halogen atom, a nitro or a
methyl group.
3. Chromium complex dyes according to claim 1 or 2,
wherein X1 is hydrogen and one of the symbols X2 and X3 is
hydrogen and the other is chlorine and nitro.
4. Chromium complex dyes according to claim 1 or 2,
of the formula
(4)
<IMG>
wherein R, R1 and Me? have the meanings assigned to them in
respect of the formula (1) in claim 1.
5. Chromium complex dyes according to claim 1 or 2,
of the formula
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<IMG> (5)
wherein R, R1 and Me? have the meanings assigned to them in
respect of the formula (1) in claim 1.
6. The chromium complex according to claim 1 or 2, of
the formula
<IMG>
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7. The chromium complex according to claim 1 or 2,
of the formula
<IMG>
- 14 -

Description

104~00~
The present invention provides novel chromium complex
dyes of the formula
I 1 ~
Cr 2Me~ (1)
L 3
wherein one of the symbols Z and Z is a nitro group and the
other is hydrogen, a nitro group, a halogen atom, a methyl, a
methoxy or an acylamino group, R is a phenyl radical which is
optionally substituted by halogen, low molecular alkyl or
nitro, Rl is a phenyl radical which is optionally substituted
by halogen, low molecular alkoxy, low molecular alkyl or by
nitro, one of the symbols, Xl, X2 and X3 is hydrogen and each
of the others is independently hydrogen, ~ nitro group, a
halogen atom, a methyl or a methoxy group and Me~ is a cation.
- 2 - ~:
.~

1049~1
By halogen is meant in this connection above all chlorine and
bromine. The term "low molecular" denotes radicals with 1 to
4 carbon atoms and "acylamino" comprises radicals such as
alkanoylamino, alkoxycarbonylamino and alkylsulphonylamino.
The novel chromium complexes are manufactured by
converting one of the azo dyes of the formula
OH ~ - N-R-SO3H
Zl ~ N = N C/ ' (2)
Z SH3
or
1 ~ N = N - C
wherein Zl' Z2' Xl, X2, X3, R and Rl have the meanings
already assigned to them, by reaction with a chromium donor
into the 1:1 chromium complex and subsequently reacting this
latter with the non-metallised dye of the formula (3) or (2)
to form the 1:2 chromium complex. Preferably, the l:l
chromium complex is manufactured from the dye of the formula
(2) and the dye of the formula (3) is added thereto.
.

104~001
The monoazo dyes of the formula (2) and (3) are
obtained in known manner by diazotisation of aminophenols and
coupling to a 3-methyl-5-pyrazolone.
Suitable coupling components for dyes of the formula
(~) are:
1-(2'- or 3'- or 4'-sulphophenyl)-3-methyl-5-pyrazolone
1-(2',5'-dichloro-4'-sulphophenyl)-3-methyl-5-pyrazolone
Suitable coupling components for dyes of the
formula (3) are:
1-(2'ethylphenyl)-3-methyl-5-pyrazolone
1-(4'-bromophenyl)-3-methyl-5-pyrazolone
1-(2'-chloro-6'-methylphenyl)-3-methyl-5-pyrazolone
1-(3'-nitrophenyl)-3-methyl-5-pyrazolone and especially
l-phenyl-3-phenyl-5-pyrazolone,
1-(2'-, 3'- or 4'-chlorophenyl)-3-methyl-5-pyrazolone
1-(2'-. 5'- or 3', 4'-dichlorophenyl)-3-methyl-5-pyrazolone
1-(2',5-dibromophenyl)-3-methyl-5-pyrazolone
1-(2',4',6'-trichlorophenyl)-3-methyl-5-pyrazolone
1-(4'-methoxyphenyl)-3-methyl-5-pyrazolone.
Suitable diazo components for dyes of the formula
(2) are:
6-nitro-4-methyl-2-amino-1-hydroxybenzene
4,6-dinitro-2-amino-1-hydroxybenzene
4-chloro-6-nitro-2-amino-1-hydroxybenzene
4-nitro-6-chloro-2-amino-1-hydroxybenzene
-- 4

1~4~9001
4-nitro-6-~cetylamino-2-amino-1-hydroxybenzene
4 -nitro-6-ethoxycarbonylamino-2-amino-1-hydroxybenzene
4-nitro-6-methanesulphonylamino-2-amino-1-hydroxybenzene
4-nitro-2-amLno-l-hydroxybenzene.
The same diazo components which are suitable for the
dyes of the formula (2) are also suitable for those of the
formula (3), as well as the following additional diazo
components:
2-~mino-1-hydroxybenzene
4-chloro-2-amino-1-hydroxybenzene
5-chloro-2-amino-1-hydroxybenzene
5-nitro-2-amino-1-hydroxybenzene
4-methyl-2-amino-1-hydroxybenzene
4-methoxy-2-amino-1-hydroxybenzene
4,6-dichloro-2-amino-1-hydroxybenzene
4-chloro-5-nitro-2-amino-1-hydroxybenzene.
The preferred diazo component in the azo dyes of the
formula (2) is:
6-nitro-4-methyl-2-amino-1-hydroxybenzene,
4,6-dinitro-2-amino-1-hydroxybenzene or
4-chloro-6-nitro-2-amino-1-hydroxybenzene.

104~01
The preferred diazo component in the dyes of the
formula (3) is:
4- or 5-chloro-2-amino-1-hydroxybenzene,
4- or 5-nitro-2-amino-1-hydroxybenzene and also
6-nitro-4-methyl-2-amino-1-hydroxybenzene.
The conversion of the dye of the formula (2) or (3)
into the 1:1 chromium complex is accomplished by conventional
methods which are known per se, for example by reacting it in
acid medium with a salt of trivalent chromium, e g.chromium for-
miate, chromium sulphate or chromium fluoride, at boiling tem-
perature or optionally at temperature exceeding 100C.It is also
possible to produce trivalent chromium in the reaction mixture
from chromium-VI compounds by simultaneously adding a reducing
agent, e.g. glucose. In general, it is advisable to carry out
the metallising in the presence of organic solvents. Preferably
the process is carried out in organic solvents such as alcohols
or ketones and as far as possible excluding water.
As a general rule it proves advantageous not to dry the
starting dyes required in the present process after their
manufacture and precipitation, but to process them further as
a moist paste.
- The reaction of the 1:1 chromium complex of the dye
of the formula (2) or (3) with the metal-free dye of the
formula (3) or (2) is desirably carried out in a medium which
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lV4.'~3()1
is neutral to weakly alkaline, in an open or a sealed vessel,
flt normal or elevated temperature, e.g. at te~peratures
~etween 50C and 120C. It is possible to carry out the
reaction in organic solvents, e.g. alcohols or ketones or in
an aqueous solution. The addition of solvents, e.g. alcohols
or dimethyl formamide, can promote the reaction if so desired.
It is normally advisable to react as far as possible equivalent
amounts of the chromium-containing 1:1 complex and of the
metal-free dye, the molecular ration between metal-free dyed and
1:1 complex being with advantage at least 0.85:1 and at most
1:0.85. A surplus of metal-containing dye is usually less
disadvantageous than one of metal-free dye. The closer this
ratio is to 1:1 the more advantageous the result generally is.
Instead of homogenous dyes of the formula (2) or (3),
lS it is also possible to use mixtures of corresponding dyes.
Interesting shades are also obtained in this way.
The novel chromium-containing mixed complexes are
advantageously isolated in the form of their salts, in
particular their alkali salts, above all sodium salts, or
also ammonium saits or salts of organic amines with positively
charged nitrogen atom, and are suitable for dyeing and
printing the most varied materials, but primarily for dyeing
nitrogenous materials, such as silk, leather, and, above all,
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~ . .

104~001
wool, as well flS synthetic fibres made from polyamides or
polyurethanes. They are suitable above all for dyeing from a
weakly fllkaline, neutral or weakly acid bath. e g. an acetic
flcid bath. The resultant dyeings are level and have good
fastness to light, washing, fulling, decatising and
carbonising.
The following Examples illustrate the invention, the
parts and percentages being by weight unless otherwise stated.

104~9S~01
EXAMPI.E 1
48.3 parts of the 1:1 chromium complex of the monoazo
dye obtflined in known manner from diazotised l-hydroxy-2-
amino-4-methyl-6-nitrobenzene coupled with 1-phenyl-3-methyl-
S-pyrazolone-4'-sulphonic acid and 33.9 parts of the monoazo
dye obtained from diazotised l-hydroxy-2-amino-5-nitrobenzene
coupled with l-phenyl-3-methyl-5-pyrazolone are stirred in
1000 parts of hot water. The batch is adjusted with 20 parts
by volume of concentrated sodium hydroxide solution to a pH
of 7 to 8 and stirred Lor 4 hou~s at 90-95C. Upon termination
of the reaction, the dye is precipitated by addition of sodium
chloride, filtered off and dried. It is a dark red powder
which gives a red solution in water and dyes wool or polyamide
in bluish red shades of good fastness properties.
_ g _

104~9001
EXAMPI.E 2
48.3. parts of the 1:1 chromium complex (1 molecule
of monoazo dye: 1 atom of chromium) of the azo dye obtained
in known manner from diazotised 6-nitro-4-methyl-2-amino-
phenol and 1-phenyl-3-methyl-5-pyrazolone-4'-sulphonic acid
are stirred together in 1000 parts of hot water with 35.3
parts of the monoazo dye obtained in known manner from
diazotised 6-nitro-4-methyl-2-aminophenyl and 1-phenyl-3-
methyl-5-pyrazolone. The suspension is adjusted to a pH of 7
to 8 by addition of 20 parts by volume of concentrated sodium
hydroxide solution and subsequently stirred at 90-95C until
it is no longer possible to detect both starting dyes. The
homogeneous chromium complex which is present in the clear
solution is precipitated by addition of sodium chloride,
isolated by filtration, washed with sodium chloride solution
~nd dried in vacuo. After it has been ground, the dye is in
the form of a dark red, readily water-soluble powder and dyes
wool or polyamide fibres from a dyebath containing ammonium
sulphate in full, red shades of good fastness properties.
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