CA1049001A - Chromium complex dyes, their manufacture and use - Google Patents
Chromium complex dyes, their manufacture and useInfo
- Publication number
- CA1049001A CA1049001A CA75217945A CA217945A CA1049001A CA 1049001 A CA1049001 A CA 1049001A CA 75217945 A CA75217945 A CA 75217945A CA 217945 A CA217945 A CA 217945A CA 1049001 A CA1049001 A CA 1049001A
- Authority
- CA
- Canada
- Prior art keywords
- nitro
- formula
- methyl
- chromium complex
- group
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
NOVEL CHROMIUM COMPLEX DYES, THEIR MANUFACTURE AND USE
Abstract of the Disclosure Chromium complex of the formula (1)
Abstract of the Disclosure Chromium complex of the formula (1)
Description
104~00~
The present invention provides novel chromium complex dyes of the formula I 1 ~
Cr 2Me~ (1) 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.
The present invention provides novel chromium complex dyes of the formula I 1 ~
Cr 2Me~ (1) 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) 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 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 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, ~ . .
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.
.~
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) 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 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 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, ~ . .
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.
Claims (7)
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.
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) 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 (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
7. The chromium complex according to claim 1 or 2, of the formula
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH61774A CH589126A5 (en) | 1974-01-17 | 1974-01-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1049001A true CA1049001A (en) | 1979-02-20 |
Family
ID=4191170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA75217945A Expired CA1049001A (en) | 1974-01-17 | 1975-01-15 | Chromium complex dyes, their manufacture and use |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS5837341B2 (en) |
| AR (1) | AR207461A1 (en) |
| AU (1) | AU7736275A (en) |
| BR (1) | BR7500264A (en) |
| CA (1) | CA1049001A (en) |
| CH (1) | CH589126A5 (en) |
| DE (1) | DE2501449C2 (en) |
| ES (1) | ES433862A1 (en) |
| FR (1) | FR2258431B1 (en) |
| GB (1) | GB1493474A (en) |
| IT (1) | IT1026342B (en) |
| NL (1) | NL7500077A (en) |
| ZA (1) | ZA75315B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH616953A5 (en) * | 1975-08-27 | 1980-04-30 | Sandoz Ag | |
| DE2840651A1 (en) * | 1978-09-19 | 1980-03-27 | Bayer Ag | CHROME COMPLEX DYES |
| DE3049552A1 (en) * | 1980-12-31 | 1982-07-29 | Basf Ag, 6700 Ludwigshafen | COMPLEX DYE MIXTURES |
| JPH03169971A (en) * | 1989-11-29 | 1991-07-23 | Matsushita Electric Works Ltd | Directly laid flooring and manufacturing method thereof |
Family Cites Families (3)
| 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 |
| FR1209088A (en) * | 1958-04-30 | 1960-02-29 | Cfmc | New azo dye chromium plating process and resulting new chromium dyes |
| FR1518833A (en) * | 1967-02-10 | 1968-03-29 | Ugine Kuhlmann | New mixed metal complexes |
-
1974
- 1974-01-17 CH CH61774A patent/CH589126A5/xx not_active IP Right Cessation
-
1975
- 1975-01-01 AR AR257306A patent/AR207461A1/en active
- 1975-01-03 NL NL7500077A patent/NL7500077A/en not_active Application Discontinuation
- 1975-01-14 FR FR7500958A patent/FR2258431B1/fr not_active Expired
- 1975-01-15 CA CA75217945A patent/CA1049001A/en not_active Expired
- 1975-01-15 DE DE2501449A patent/DE2501449C2/en not_active Expired
- 1975-01-15 BR BR264/75A patent/BR7500264A/en unknown
- 1975-01-15 IT IT47680/75A patent/IT1026342B/en active
- 1975-01-16 ZA ZA00750315A patent/ZA75315B/en unknown
- 1975-01-16 ES ES433862A patent/ES433862A1/en not_active Expired
- 1975-01-16 AU AU77362/75A patent/AU7736275A/en not_active Expired
- 1975-01-16 GB GB1935/75A patent/GB1493474A/en not_active Expired
- 1975-01-17 JP JP50007197A patent/JPS5837341B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU7736275A (en) | 1976-07-22 |
| DE2501449A1 (en) | 1975-07-24 |
| AR207461A1 (en) | 1976-10-08 |
| JPS5837341B2 (en) | 1983-08-16 |
| IT1026342B (en) | 1978-09-20 |
| JPS50102623A (en) | 1975-08-14 |
| DE2501449C2 (en) | 1983-11-24 |
| ES433862A1 (en) | 1976-12-01 |
| CH589126A5 (en) | 1977-06-30 |
| FR2258431B1 (en) | 1977-07-01 |
| ZA75315B (en) | 1976-01-28 |
| BR7500264A (en) | 1975-11-04 |
| GB1493474A (en) | 1977-11-30 |
| NL7500077A (en) | 1975-07-21 |
| FR2258431A1 (en) | 1975-08-18 |
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