CA1049000A - Chromium complex dyes, their manufacture and use - Google Patents
Chromium complex dyes, their manufacture and useInfo
- Publication number
- CA1049000A CA1049000A CA75217832A CA217832A CA1049000A CA 1049000 A CA1049000 A CA 1049000A CA 75217832 A CA75217832 A CA 75217832A CA 217832 A CA217832 A CA 217832A CA 1049000 A CA1049000 A CA 1049000A
- Authority
- CA
- Canada
- Prior art keywords
- nitro
- methyl
- chromium
- dye
- chromium complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
- C09B45/16—Monoazo compounds containing chromium
Abstract
NOVEL CHROMIUM COMPLEX DYES, THEIR MANUFACTURE AND USE
Abstract of the Disclosure Chromium complex dyes of the formula (I)
Abstract of the Disclosure Chromium complex dyes of the formula (I)
Description
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
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:
' -' ' ' '' ' '' ' ' 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:
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
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:
' -' ' ' '' ' '' ' ' 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 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
The preferred aminophenols are those which carry 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 .. . -- - ' ~ ' :
. ' : ' 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 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 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:
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 _ 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:
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 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 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.
_ 13 -- ~
., :
' . , `' ', ' , ~
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 .. . -- - ' ~ ' :
. ' : ' 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 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 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:
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 _ 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:
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 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 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.
_ 13 -- ~
., :
' . , `' ', ' , ~
Claims (6)
1. Chromium complex dyes of the formula (I) wherein Z is a nitro group or a chlorine atom, each of R and R1 is a phenyl radical which is optionally substituted by halogen, low molecular alkoxy, low molecular alkyl or nitro, one of the symbols X1, 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.
2. Chromium complex dyes according to claim 1, wherein one of the symbols X1, X2 and X3 is a nitro group.
3. Chromium complex dyes according to claim 1, wherein X1 is hydrogen and one of the symbols X2 and X3 is nitro and the other is hydrogen.
4. Chromium complex dyes according to claim 1, wherein X1 is nitro, X2 is hydrogen and X3 is methyl or chlorine.
5. The dye according to claims 1 to 3, of the formula
6. The dye according to claims 1, 2 and 4, of the formula
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH50674A CH583285A5 (en) | 1974-01-15 | 1974-01-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1049000A true CA1049000A (en) | 1979-02-20 |
Family
ID=4188557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA75217832A Expired CA1049000A (en) | 1974-01-15 | 1975-01-13 | Chromium complex dyes, their manufacture and use |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS5839183B2 (en) |
| AR (1) | AR218427A1 (en) |
| AU (1) | AU7681774A (en) |
| BR (1) | BR7500117A (en) |
| CA (1) | CA1049000A (en) |
| CH (1) | CH583285A5 (en) |
| DE (1) | DE2501039C2 (en) |
| ES (1) | ES433766A1 (en) |
| FR (1) | FR2257657B1 (en) |
| GB (1) | GB1492683A (en) |
| IT (1) | IT1026317B (en) |
| NL (1) | NL7417051A (en) |
| ZA (1) | ZA75245B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH616953A5 (en) * | 1975-08-27 | 1980-04-30 | Sandoz Ag | |
| DE2835493C2 (en) * | 1978-08-12 | 1983-05-19 | Bayer Ag, 5090 Leverkusen | Chromium complex dyes |
| DE4130806A1 (en) * | 1991-09-17 | 1993-03-18 | Bayer Ag | UNBALANCED 1: 2 CHROME COMPLEX DYES |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB765355A (en) * | 1953-06-08 | 1957-01-09 | Ciba Ltd | Mixed complexes of metalliferous mono-azo-dyestuffs and process for making them |
| DE1133846B (en) * | 1958-04-30 | 1962-07-26 | Ciba Geigy | Process for the production of chromium-containing azo dyes |
| FR1297014A (en) * | 1960-08-09 | 1962-06-22 | Basf Ag | Ammonium salts of metal complex dyes |
| DE1271857B (en) * | 1962-10-17 | 1968-07-04 | Ciba Geigy | Process for the production of chromium-containing azo dyes |
-
1974
- 1974-01-15 CH CH50674A patent/CH583285A5/xx not_active IP Right Cessation
- 1974-12-24 AU AU76817/74A patent/AU7681774A/en not_active Expired
- 1974-12-31 NL NL7417051A patent/NL7417051A/en not_active Application Discontinuation
-
1975
- 1975-01-08 BR BR117/75D patent/BR7500117A/en unknown
- 1975-01-13 IT IT47644/75A patent/IT1026317B/en active
- 1975-01-13 GB GB1376/75A patent/GB1492683A/en not_active Expired
- 1975-01-13 DE DE2501039A patent/DE2501039C2/en not_active Expired
- 1975-01-13 CA CA75217832A patent/CA1049000A/en not_active Expired
- 1975-01-13 FR FR7500877A patent/FR2257657B1/fr not_active Expired
- 1975-01-14 AR AR257283A patent/AR218427A1/en active
- 1975-01-14 ZA ZA00750245A patent/ZA75245B/en unknown
- 1975-01-14 ES ES433766A patent/ES433766A1/en not_active Expired
- 1975-01-14 JP JP50005995A patent/JPS5839183B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CH583285A5 (en) | 1976-12-31 |
| DE2501039A1 (en) | 1975-07-17 |
| GB1492683A (en) | 1977-11-23 |
| DE2501039C2 (en) | 1983-10-27 |
| JPS5839183B2 (en) | 1983-08-27 |
| NL7417051A (en) | 1975-07-17 |
| ES433766A1 (en) | 1976-12-16 |
| IT1026317B (en) | 1978-09-20 |
| ZA75245B (en) | 1976-01-28 |
| FR2257657A1 (en) | 1975-08-08 |
| FR2257657B1 (en) | 1977-07-01 |
| JPS50102622A (en) | 1975-08-14 |
| AU7681774A (en) | 1976-06-24 |
| AR218427A1 (en) | 1980-06-13 |
| BR7500117A (en) | 1975-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1059997A (en) | Chromium complex dyes, their manufacture and use | |
| CA1049000A (en) | Chromium complex dyes, their manufacture and use | |
| CA1088051A (en) | Chromium complex dyes, process for their manufacture and use thereof | |
| US4083839A (en) | Unsymmetrical mono sulfo containing 1:2 azo, azo chromium complex dyes | |
| US3221003A (en) | Chrgmium cqmplex mixed azo dyestuffs | |
| CA1049001A (en) | Chromium complex dyes, their manufacture and use | |
| CA1048494A (en) | Chromium complex dyes, their manufacture and use | |
| US3067191A (en) | chschohchaoh | |
| US4424152A (en) | Metal complex dyestuffs, processes for their preparation and their use for dyeing nitrogen-containing materials | |
| US4053462A (en) | Unsymmetrical phenyl azo naphthyl chromium complex dyes | |
| US4997917A (en) | Preparation of 1:2 chromium complex azo dyes asymmetrically substituted with solubilizing | |
| US4113719A (en) | 1:2-Cobalt-complex azo dyestuffs having an acetoacetylamino diphenylamino coupler | |
| US3511827A (en) | Metallized monoazo dye for nylon | |
| US4499015A (en) | Chromium complex azo dyestuffs and mixtures of chromium complex azo dyestuffs derivated from 1-amino-2-hydroxynaphtalene-4-sulphonic acids or aminophenols | |
| US2829139A (en) | Metalliferous azo dyestuff | |
| US3925346A (en) | Mixed chromium-containing azo dyestuffs containing, per atom of chromium, one molecule of an o,o'-dihydroxy-sulphophenylene-azo-naphthalene and one molecule of an -o-hydroxyphenylene-azo-acetoacetamide | |
| US2809962A (en) | Cobalt complex azo dyestuff | |
| CA1159051A (en) | Fibre-reactive chromium complex dyes, process for their production and use thereof | |
| US3492287A (en) | Monoazo heterocyclic dyestuffs | |
| US4013630A (en) | Chromium complex disazo dyes | |
| US3040020A (en) | Metal complex of x-cyanonaphtkyl- | |
| CA1047486A (en) | Chromium complex dye, its manufacture and use | |
| US3169951A (en) | Chromhjm-containing azo dyestuffs | |
| GB2027734A (en) | Chromium complex dyestuffs | |
| US2709698A (en) | Azo dyes derived from hydroquinone mono-ethers |