Patent GB-737619-A (GB)
Title: Improvements relating to metallisable monoazo dyestuffs and their complex heavy metal compounds
IPC: C09B62/515
Filed: 1953-07-14
Abstract: The invention comprises (1) monoazo dyestuffs containing an o : o1-dihydroxy or o-hydroxy-o1-carboxy grouping (or one convertible thereto under metallizing conditions) and an aromatically bound -SO2-CH2-Cl group in the diazo and/or coupling component residues, but otherwise free from solubilizing groups; and processes for the production of such dyestuffs; (2) the metallization of the dyestuffs in substance or on the fibre; and (3) complex cobalt and chromium derivatives of dyestuffs 2 - amino - 4 - chlormethylsulphonylphenol-->component coupling oto a hydroxyl group and free from solubilizing groups. Metallization in substance can be carried out with cobalt nitrate, cobalt sulphate, cobalt acetate or complex chromic salts, e.g. alkali chromosalicylates.  The metallized dyestuffs can be mixed with alkaline-reacting salts such as sodium carbonate or phosphate and with wetting or dispersing agents.  They dye wool, silk, polyamide, polyurethane, casein, leather, feathers and other protein materials from a neutral or weakly acid bath.  Examples describe the preparation of the following: (1) the dyestuff 2 - amino - 4 - chloromethylsulphonylbenzoic acid-->1 - (m - chlorophenyl) - 3-methyl-5-pyrazolone and its chromium compound; (2) 2-amino-4-chloromethylsulphonylphenol-->acetoacetic anilide and its chromium and cobalt derivatives; (3) 2-amino-4-chloromethylsulphonyl - phenol-->1 - (m - chlorophenyl) - 3 - methyl - 5 - pyrazolone and chromium derivative; (4) 2-amino-4-chloromethylsulphonyl - phenol-->1 - (m - chlorophenyl) - 5 - pyrazolone - 3 - carboxylic amide and chromium compound; (5) 2-amino-4-chloromethylsulphonyl - phenol-->1 - formylamino-7-naphthol and chromium derivative; (6) 2 - amino - 4 - chloromethylsulphonyl - 6-nitrophenol-->b -naphthol and chromium compound.  Further examples show the dyeing of wool with (3) and (5) by the metachrome process.  A table is given showing as additional coupling components p-cresol, 2-acetylamino-p-cresol, acetylaminonaphthol, naphtholmethylsulphone, naphtholsulphonamide, 2 : 4-dihydroxyquinoline, 1 : 3-dihydroxy-isoquinoline and 1 - (m - chloromethylsulphonyl - phenyl)-3 - methyl - 5 - pyrazolone.  Other suitable diazo p  compounds are o-aminonaphthols, o-aminonaphthoic acids, o-halogen-anilines and o-alkoxy-anilines.  Both components may contain halogen, alkyl, alkoxy, aryloxy, nitro, acylamino, sulphone and sulphonamide substituents.  Specifications 667,168, 730,036 and 736,034 are referred to.ALSO:Dyestuff intermediates containing chloromethyl-sulphonyl groups attached to aromatic nuclei are made by reacting arylsulphinic acids with dichloracetic acid, decarboxylation taking place.  Amino groups in the products can then be (1) reacted with ketene to give acetoacetic arylides or (2) diazotized, reduced to hydrazino and condensed with acylacetic esters to form pyrazolones.  In an example toluene-p-sulphinic acid is condensed with dichloracetic acid to give toluene-p-chloromethylsulphone; this is converted successively by nitration to 2-nitro-4-chloromethyl-sulphonyl-toluene, reduction to 2 - amino - 4 - chloromethylsulphonyltoluene, acylation to 2-acetamido-4-chloromethylsulphonyl - toluene, oxidation to 2-acetamido - 4 - chloromethylsulphonylbenzoic acid and final hydrolysis to 2-amino-4-chloromethylsulphonyl-benzoic acid. Other compounds mentioned are 2-amino-4-chloromethylsulphonyl - phenol, 2 - amino - 4 - chloromethylsulphonyl - 6 - nitrophenol (by direct nitration) and 1 - (m - chloromethylsulphonylphenyl) - 3 - methyl - 5 - pyrazolone and the corresponding 3-phenyl, 3-carbalkoxy and 3-carboxylic amide compounds.