Note: Descriptions are shown in the official language in which they were submitted.
1049000
The present invcntion provides novel chromium com-
plex dyes Or thc ~ormu]a
~ S03~ C -
~C3N
Cl \ Me (1)
L 1~ i N c~c;~ ~
wherein Z is a nitro group or a chlorine atom, each of R
and Rl is a phenyl radical which is optionally substituted
by halogen, low molecular alkoxy, low molecular alkyl or ni-
tro, one of the symbols Xl, X2 and X3 is hydrogen and each
of the others is hydrogen, a halogen atom, a nitro, methyl
or methoxy group and Me+ is a cation. By halogen is meant
in this connection above all chlorine and bromine and the
term "low molecular" denotes radicals with 1 to 4 carbon
atoms.
The novel chromium complex dyes are manufactured
by converting one of the azo dyes of the formula
~049WO
HO
~H ~C-N-R
Z ~ _ N = N - ~ I (2)
&
C~l
S031~ 3
or
HO
Xl ~ N N C/~ 1 1 (3)
X2 ~ ~=N
X3 CH3
into the 1:l chromium complex by reaction with a chromium
donor and subsequently reacting this compound with the non-
metallised dye of the formula (3) or (2) to give the 1:2
chromium complex.
Preferably, the 1:1 chromium complex is manufac-
tured from the dye of the formula (2) and the dye of the
formula (3) is added thereto.
The monoazo dyes of the formula (2) are obtained
in known manner by coupling diazotised 2-amino-1-hydroxy-
4-sulpho-6-nitrobenzene or 2-amino-1-hydroxy-4-sulpho-6-
chlorobenzene to a l-phenyl-3-methyl-5-pyrazolone and those
of the formula (3) by coupling a diazotised aminophenol to
a l-phenyl-3-methyl-5-pyrazolone.
Examples of suitable coupling components for dyes
of the formula (2) or (3) are:
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'
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1-(2'-ethyl~ eny])-3-methyl-5-pyrazolone
1-(4'-bromophenyl)-3-methyl-5-pyraæolone
1-(2'-chloro-6'-methylphenyl)-3-methyl-5-pyrazolone
1-(3'-ni.trophenyl)-3-methyl-5-pyrazolone and especially
1-phenyl-3-~ethyl-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
(3) are:
2-amino-1-hydroxybenzene
4- or 5-chloro-2-amino-1-hydroxybenzene
4- or 5-ni.tro-2-amino-1-hydroxybenzene
4-methyl-2-amino-1-hydroxybenzene
4-methoxy-2-amino-1-hydroxybenzene
4,6-dichloro-2-amino-1-hydroxybenzene
4,6-dinitro-2-amino-1-hydroxybenzene
20~ 4-chloro-5-nitro-2-amino-1-hydroxybenzene
4-chloro-6-nitro-2-amino-1-hydroxybenzene
6-chloro-4-nitro-2-amino-1-hydroxybenzene
6-nitro-4-methyl-2-amino-1-hydroxybenzene.
The preferred aminophenols are those which carry
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a nitro group, especially 4- or 5-nitro-2-amino-1-hydroxy-
ben~ene ancl 6-nitro-4-methyl or 4-chloro-2-amino-1-hydroxy-
ben~cne.
The conversion of the dyes of the formula (2) or
(3) into the 1:1 chromium complex is accomplished by con-
ventional methods which are known per se, e.g. by reacting
it in an acid medium with a salt of trivalent chromium, e.g.
chromium formate, chromium sulphate, chromium chloride hexa-
hydrate or chromium fluoride, at boiling temperature or op-
tionally at temperatures exceeding 100C. Trivalent chromium
can also be manufactured in the reaction mixture from chro-
mium-(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
e.g. alcohols or ketones, and as far as possible excluding
water.
It is normally 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 neutral to
weakly alkaline medium, in an open or a sealed vessel, and at
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normal or elevatcd temperature, e.g. at temperatures between
50 and 120C. The process can be carried out in organic sol-
vents, e.g. alcohols or ketones or in an aqueous solution, in
which case the addition of solvents, e.g. alcohols, dimethyl
S formamide, can promote the reaction if so desired. It is usu-
ally advisable to react as far as possible equivalent amounts
of the chromium-containing 1:1 complex and the metal-free
dye, the molecular ratio between metal-free dye and 1:1 com-
plex being desirably at least 0.85:1 and at most 1:0.85. A
surplus of metal-containing dye is usually less disadvantage-
ous than Otle of metal-free dye. The closer this ratio is to
1:1 the more advantageous the result generally is.
Instead of homogeneous dyes of the formula (2) or
(3), it is also possible to use mixtures of corresponding
dyes. In this way, interesting shades are often obtained.
The novel chromium-containing mixed complexes ob-
tained by the above processes are isolated with advantage in
the form of their salts, in particular alkali salts, above
all sodium salts, or also ammonium salts or salts of organic
amines with positively charged nitrogen atoms, and are suit-
able for dyeing and printing the most varied materials, but
chiefly for dyeing materials made from natural polyamides,
such as silk, leather, and especially wool as well as for
dyeing and printing synthetic polyamide fibres, e.g. fibres
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1049000
made from polyamides or polyurethanes. They are mainly suit-
able for dyeing from a weakly alkaline, neutral or weakly
acid bath, for example from an acetic acid bath.
Thc resultant dyeings are level and have good fast-
ness to light, washing, fulling, decatising, and carbonising.
The following Examples illustrate the invention,
the parts and percentages being by weight unless otherwise
stated
1049000
Example 1
46.9 par~-s of thc 1:1 chromium complex (i.e. containing 1
atom of chromium: 1 molecule of monoazo dye) of the azo dye
obtained in known manner from diazotised 6-nitro-2-amino-
phenol-4-sulphonic acid and 1-phenyl-3-methyl-5-pyrazolone
and 33.9 parts of the monoazo dye obtained in known manner
from diazotised 5-nitro-2-aminophenol and 1-phenyl-3-methyl-
5-pyrazolone are stirred in 1000 parts of hot water. The re-
sultant suspension is adjusted to a pH of 7 to 8 by addition
of 20 parts by volume of concentrated sodium hydroxide solu-
tion and subsequently stirred until it is no longer possible
to detect both starting dyes. The homogeneous chromium mixed
complex present in the clear solution is precipitated by ad-
dition of sodium chloride, isolated by filtration, washed
with sodium chloride solution and 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, bluish red
shades of good fastness properties
Example 2
46;9 parts of the 1:1 chromium complex (1 atom of chromium:
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1 mo]ecule o~ monoazo dye) of the azo dye obtained in known
manner from diazotised 6-nitro-2-aminoyhenol-4-sulphonic acid
and l-phcny]-3-methyl-5-pyrazo]one and 38.75 parts of the
monoazo dyc obtaincd itl known manner from diazotised 6-ni-
tro-4-methyl-2-aminophenol and 1 (3'-chlorophenyl)-3-methyl-
5-pyrazolone are stirred in lO00 parts of hot water. The re-
sultant suspension is adjusted to a pH of 7 to 8 by addition
of 20 parts by volume of concentrated sodium hydroxide solu-
tion and subsequently stirred at 90C-95C until it is no
longer possible to detect both starting dyes. The homogeneous
chromium mixed complex present in the clear solution is iso-
lated by addition of sodium chloride, isolated by filtration,
washed with sodium chloride solution and dried in vacuo. Af-
ter it has been ground, the dye is in the form of a dark red
readily water-soluble powder and dyes wool or polyamide fi-
bres from a dyebath containing ammonium sulphate in full, red
shades of good fastness properties.
Example 3
46.9 parts of the 1:1 chromium complex (1 atom of chromium:
1 molecule of monoazo dye) of the azo dye obtained in known
manner from diazotised 6-nitro-2-aminophenol-4-sulphonic acid
and l-phenyl-3-methyl-5-pyrazolone and 33.9 parts of the mono-
g _
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azo dyc obtained in l~nown manner from diazotised 4-nitro-2-
aminophcnol and l-phenol-3-methyl-5-pyrazolone are stirred
in 1000 parts of hot water. The resultant suspension is ad-
justed ~o a pH of 7 to 8 by addition of 20 parts of concentra-
S ted sodium hydroxide solution and subsequen~ly stirred at 90-
95C until it is no longer possible to detect both starting
dyes. The homogeneous chromium mixed complex present in the
clear solution is isolated by addition of sodium chloride,
isolated by filtration, washed with sodium chloride solution
and 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, reddish orange shades of good fastness pro-
perties.
A homogeneous mixed complex which dyes wool or polyamide fi-
bres from a weakly acid bath in full, scarlet shades is ob-
tained by reacting with the above mentioned l:l chromium com-
plex 36.3 parts of the monoazo dye obtained from diazotised
2-aminophenol and 1-2',5'-dichlorophenyl-3-methyl-5-pyrazo-
lone instead of the metal-free azo dye used in this Example.
Example 4
46.9 parts of the 1:1 chromium complex (l atom of chromium:
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l molecule of monoazo dye) of ~he azo dye obtained in known
mannc~r Lrom di~otised 6-ni~ro-2-aminophenol-4-sulphonic acid
and l-phenyl-3-methyl-5-pyrazolone and 35.3 parts of the mono-
aæo dye ob~ained in known manner from diazotised 6-nitro-4-
S methyl-2-aminophenol and 1-phenyl-3-methyl-5-pyrazolone are
stirred in lO00 parts of hot water The resultant suspension
is adjusted to a pH of 7 to 8 by addition of 20 parts by volu-
me 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 mixed complex
pres~nt in the clear solution is precipitated by addition of
sodium chloride, isolated by filtration, washed with sodium
chloride solution and 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 con-
taining ammonium sulphate in full, red shades of good fast-
ness properties.
Example 5
40.85 parts of the 1:1 chromium complex (1 atom of chromium:
1 molecule of monoaæo dye) of the azo dye obtained in known
manner from diazotised 6-chloro-2-aminophenol-4-sulphonic
acid and l-phenyl-3-methyl-5-pyrazolone and 33.9 parts of the
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monoazo dye ob~ined in known manner from diazotised 4-nitro-
2-amin()phenol and 1-phe~yl-3-methyl-5-pyrazolone are stirred
in 1000 parts of water. Thc resultanL suspension is adjusted
to a pll of 7 to 8 by addition of 20 parts by volume of sodium
hydroxide solution and subsequently stirred at 90-95C un-
til it is no longer possible to detect the starting dyes. The
homogeneous chromium mixed complex is precipitated by addi-
tion of sodium chloride, isolated by filtration, washed with
sodium chloride solution and dried in vacuo. After it has
been ground, the dye is in the ~orm of a dark red, readily
water-soluble powder and dyes wool or polyamide fibres from
a dyebath containing ammonium sulphate in full, yellowish
orange shades of good fastness properties.
Example 6
46.9 parts of the 1:1 chromium complex (l atom of chromium:
1 molecule of monoazo dye) of the azo dye obtained in known
manner from diazotised 6-nitro-2-aminophenol-4-sulphonic acid
and l-phenyl-3-methyl-5-pyrazolone, 16.95 parts of the mono-
azo dye obtained in known manner from diazotised 4-nitro-2-
aminophenol and 1-phenyl-3-methyl-5-pyrazolone and 17.65 parts
of the monoazo dye obtained from diazotised 6-nitro-4-methyl-
2-aminophenol and 1-phenyl-3-methyl-5-pyrazolone are stirred
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in 100 parts of hot water. The resultant suspension is ad-
justed to a p~l of 7 to 8 and subsequently stirred at 90-95C
until it is no longer possible to deitect any of the starting
dyes. The chromium mixed complexed present in clear solution
are precipitated by the addition of sodium chloride, isolated
by filtration, washed with sodium chloride solution and dried
in vacuo.
After it has been ground, the novel dye is in the form of a
red, readily water-soluble powder and dyes wool or polvamide
from a dyebath containing ammonium sulphate in full, fast
scarlet shades.
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., :
' . , `' ', '
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