Claims
- 1. A water-soluble copper complex disazo dyestuff of the formula ##STR18## wherein A is phenyl, phenyl substituted by methoxy or carboxy or naphthyl, C is phenylene, phenylene substituted by methoxy or phenylene substituted by lower alkyl, C and C' together are naphthylene, B is naphthylene or naphthalene substituted by amino, acetylamino or benzoylamino, m is 1, 2, 3, 4, 5 or 6, Y is --SO.sub.2 --CH.dbd.CH.sub.2, --NH--SO.sub.2 CH.dbd.CH.sub.2 or --SO.sub.2 --CH.sub.2 --Z wherein Z is hydroxy, methylsulfonyloxy, p-tolysulfonyloxy, acetoxy, dimethylamino, diethylamino, thiosulfato, phosphato or sulfato and P is 1 or 2, or 1 or 2 or 3 where Y is .beta.-hydroxy-ethyl-sulfone sulfuric acid ester.
- 2. A water-soluble copper complex disazo dyestuff of the formula ##STR19## wherein A is phenyl or naphthyl, C is phenylene or phenylene substituted by lower alkyl, C and C' together are naphthylene, B is naphthylene, m is 1, 2 or 3 and Y, being substituted in A or C' only, is --SO.sub.2 --CH--CH.sub.2 or --SO.sub.2 --CH.sub.2 --CH.sub.2 --Z wherein Z is hydroxy, methylsulfonxyloxy, p-tolysulfonyloxy, acetoxy, dimethylamino, diethylamino, thiosulfato, phosphato or sulfato.
- 3. A water-soluble copper complex disazo dyestuff according to claim 1 of the formula ##STR20## wherein A, B, C, C' and m have the meanings given in claim 2 and Y is the group of the formula
- --SO.sub.2 --CH.sub.2 --CH.sub.2 --O--SO.sub.3 H
- bound to A or C'.
- 4. The copper complex disazo dyestuff of the formula ##STR21##
- 5. The copper complex disazo dyestuff of the formula ##STR22##
- 6. The copper complex disazo dyestuff of the formula ##STR23##
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 2047025 |
Sep 1970 |
DEX |
|
Parent Case Info
This application is a continuation-in-part application of U.S. Patent Application Ser. No. 516,093 filed Oct. 18, 1974, now abandoned, which application was a continuation-in-part application of U.S. Patent Application Ser. No. 182,884 filed Sept. 22, 1971.
The present invention relates to new water-soluble, reactive disazo dyestuffs of the formula (1) ##STR2## and copper, cobalt or chromium complex disazo dyestuffs thereof which in the metal-free form correspond to the formula (2) ##STR3## wherein A represents the radical of a diazo component of the benzene or naphthalene series, T is hydrogen or a hydroxyl, carboxyl or low-molecular-weight alkoxy group, X is hydroxyl or carboxyl, B represents the radical of a coupling component of the benzene, naphthalene or pyrazolone series, D is a bivalent bridging member and Y is a group of the formula (3)
The present invention also relates to a process for preparing these dyestuffs, which comprises diazotizing an aminoazo dyestuff of the formula (5) ##STR4## in which A, C, C', T and X have the above meanings, and coupling with an equimolar amount of a coupling component of the formula (7) ##STR5## wherein B is as defined above; the components are chosen in the way that the resulting disazo dyestuff contains, besides 1 to 6 sulfonic acid groups, 1 to 3 substituents of the formula (3) or (4), if desired bound by the bridging member D. In order to obtain their metal complex compounds, the disazo dyestuffs thus prepared may be reacted with copper-yielding agents, optionally under the conditions of the oxydative or disalkylating coppering, or with a cobalt-or chromium-yielding agent. In the case of the metal-free or metal-containing disazo dyestuffs thus obtained, the hydroxyl group of the group --SO.sub.2 --CH.sub.2 --CH.sub.2 --OH may be esterified, if desired, subsequently with sulfuric acid or with a compound yielding sulfur trioxide.
As organic or inorganic radicals Z capable of being split off by an alkaline agent, there may be mentioned the following compounds: the ester group of the alkyl or arylsulfonic acids such as the methylsulfonyloxy or the p-toluene-sulfonyloxy group; acyloxy groups such as the acetoxy group or the 3-sulfobenzoyl-oxy group; dialkylamino groups such as the dimethyl or the diethylamino group; furthermore the ester group of the thiosulfuric acid or of the phosphoric acid and especially of the sulfuric acid.
As bivalent bridging member there may be mentioned for example the following groups: ##STR6## wherein R stands for a low-molecular-weight alkyl radical or preferably for hydrogen, and wherein n stands for an integer of from 1 to 6.
The diazo and coupling components being the basis of the radical A and the radical B in formulae in (1) and (2) may contain further substituents usual in azo dyestuffs, such as halogen atoms, lower alkyl, lower alkoxy, carboxylic acid, nitro and acylamino groups.
The substituents which may be contained in the nucleus C or C' are preferably halogen atoms such as flourine or chlorine atoms, alkyl radicals such as methyl, ethyl or propyl groups as well as lower alkoxy groups such as methoxy or ethoxy groups. Suitable metal-yielding agents are for example the water-soluble copper, cobalt and chromium salts, as for example sulfates, chlorides, acetates, formiates and the salts of organic sulfonic acids.
For converting the above-obtained o,o'-dihydroxy-disazodyestuffs of the formula (1) into their metal complex compounds, the copper, cobalt and chromium compounds are advantageously reacted in a slightly acidic aqueous solution or in an organic medium for example in formamide. In the case of the disazo dyestuffs of the formula (1) which contain an o-hydroxy-o'-alkoxy-azo group, the metallization is effected under conditions which convert the alkoxy group bound in an o-position with regard to the azo group, into a hydroxyl group, for example by heating for rather a long time in the presence of copper salts and aqueous ammonia in excess.
For avoiding undesired secondary reactions of the groups of the formulae (3) or (4) contained in the starting dyestuffs of the formula (1), it is generally necessary to find out in each case the best metallization process.
The disazo or metal-complex disazo dyestuffs is effected by salting out, for example with sodium or potassium chloride or by spray drying the preparation mixture.
Preferably, the dyestuffs are water-soluble copper complex disazo dyestuffs of the formula ##STR7## wherein A is phenyl or naphthyl, C is phenylene or phenylene substituted by lower alkyl, C and C' together are naphthylene, B is naphthylene, m is 1, 2, 3, 4, 5 or 6 and Y is --SO.sub.2 --CH.dbd.CH.sub.2 or --SO.sub.2 --CH.sub.2 --CH.sub.2 --Z wherein Z is hydroxy, methylsulfonyloxy, p-tolylsulfonyloxy, acetoxy, dimethylamino, diethylamino, thiosulfato, phosphato or sulfato. Also desirable are those compounds wherein Y is a group of the formula
The dyestuffs according to the invention may be used for dyeing textile materials. They are distinguished by a high tinctorial strength and are suitable, for example, for dyeing wool, silk and polyamide fibres; they are employed from an acidic, neutral or slightly alkaline dyebath. They are particularly valuable as "reactive dyestuffs" for dyeing cotton and other natural or regenerated cellulose fibres. For dyeing these materials, the dyestuffs are used according to printing and dyeing processes in relation with a treatment with an acid-binding agent such as sodium hydroxide, sodium carbonate or sodium bicarbonate. According to this process above all cellulose textile materials may be dyed in intense shades: navy blue, grey or black, brown, red brown or in similar shades which exhibit a much better fastness to washing than dyeings of a comparable shade and prepared by the use of direct dyestuffs. The dyeings and prints obtained with the use of the novel dyestuffs of this invention show an equal and level shade and a good colour-build-up. They have good to very good fastnesses to light in the dry and wet state, to alkali, to acid, to water, to washing, also to washing in the presence of sodium perborate or sodium hypochlorite, to alkaline and acid perspiration, to fulling and cross-dyeing, to steaming, ironing and rubbing, to chlorinated bath-water, to mercerizing, to vulcanizing, to discharge, for example to sodium dithionite, and to the action of solvents.
The following Examples illustrate the invention. Parts and percentages are by weight, unless stated otherwise. The relationship between "parts by weight" and "parts by volume" is "grams" and "cubic centimeters".
US Referenced Citations (8)
| Number |
Name |
Date |
Kind |
|
3135730 |
Heyna et al. |
Jun 1964 |
|
|
3364194 |
Meininger et al. |
Jan 1968 |
|
|
3445450 |
Meininger et al. |
May 1969 |
|
|
3457251 |
Meininger |
Jul 1969 |
|
|
3457252 |
Meininger et al. |
Jul 1969 |
|
|
3518245 |
Meininger et al. |
Jun 1970 |
|
|
3637645 |
Meininger et al. |
Jan 1972 |
|
|
3655642 |
Meininger et al. |
Apr 1972 |
|
Foreign Referenced Citations (3)
| Number |
Date |
Country |
| 2047025 |
Mar 1972 |
DEX |
| 1106244 |
Mar 1968 |
GBX |
| 1134947 |
Nov 1968 |
GBX |
Continuation in Parts (2)
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Number |
Date |
Country |
| Parent |
516093 |
Oct 1974 |
|
| Parent |
182884 |
Sep 1971 |
|
Patent Grant
4185012
