Patent GB-823945-A (GB)
Title: Improvements relating to metallisable monoazo dyestuffs, of the benzene-azo naphthalene series, complex heavy metal compounds thereof, and their use
IPC: C09B45/14
Filed: 1956-02-10
Abstract: 1 - Acylamino - 8 - naphthols having in the 6-position a group R-SO2- wherein R is a possibly substituted hydrocarbon radical or an amino group which may be substituted on the nitrogen atom are used as coupling components in the preparation of azo dyestuffs (see Group IV (a)).  They are obtained from 1-amino-8-naphthol-6-sulphonic acid by protecting the amino and hydroxy groups, for example by phosgenation to form the corresponding perinaphthoxazinone, the sulphonic acid group is converted in known manner to the sulphonic acid halide group, which is then reacted with ammonia or an amine, or reduced to the sulphinic acid and alkylated, or condensed 'with aromatic hydrocarbons by the Friedel Crafts reaction.  The sulphone or sulphonamide thus obtained is saponified with alkali and the amino group is acylated.  Specified compounds are 1-acetylamino-8-naphthol-6-sulphonamide or - sulphomethylamide or - sulphodimethylamide or -sulphonic acid anilide or -sulphonic acid - N - ethyl anilide or - methylsulphone, 1-propionylamino - 8 - naphthol - 6 - sulphopropylamide or - sulphonic acid anilide, 1 - ethoxyacetylamino - 8 - naphthol - 6 - sulphonamide, 1 - carbomethoxyamino - or - carboethoxyamino - 8 - naphthol - 6 - sulphamide, 1-methanesulphonylamino - 8 - naphthol - 6 - sulphonic acid morpholide, 1 - p - toluenesulphonylamino - 8 - naphthol - 6 - sulphonic acid piperidide, 1 - benzoylamino - 8 - naphthol - 6-sulphonic acid ethanolamide or - phenylsulphone, 1 - ureido - 8 - naphthol - 6 - sulphamide, 1 - benzenesulphonylamino - 8 - naphthol - 6 - phenylsulphone, 1 - b  - chloropropionylamino - 8 - naphthol - 6 - sulphonic acid ethanolamide and 1 - ethylsulphonylamino - 8 - naphthol-6-sulphamide.  Reference has been directed by the Comptroller to Specifications 637,404, [Group IV(c)], 667,168, 712,037, 736,034, [Group IV (c)], 737,619, 743,583 and 774,884.ALSO:The invention comprises the metallizable monoazo dyes of formula <FORM:0823945/IV(c)/1> wherein A is a phenyl radical, X is a metallizable group or a substituent convertible thereto during metallization ortho to -N=N-, Y is an acyl group, R is a possibly substituted hydrocarbon radical or an amino group which may be substituted at the nitrogen atom and wherein the naphthalene coupling component is free from water-solubilizing groups which dissociate acid in neutral water, and heavy metal complexes thereof containing 1 atom of heavy metal linked to two molecules of dyestuff.  The dyes are prepared by coupling a suitably substituted benzene diazonium compound with a 1-acylamino - 8 - hydroxynaphthalene - 6 - sulphone or -sulphonamide (see Group IV (b)).  The preferred dyestuffs are those wherein the diazo component contains, with the exception of any carboxyl group taking part in the complex formation, no water-solubilizing groups which dissociate acid in neutral water. Specified diazo components, other than those in examples are 2-aminophenol-4-sulphonic acid, 6-chloro-2-aminophenol - 4 - sulphonic acid, 4 - acetyl - or ethylsulphonyl - 2 - aminophenol - 6 - sulphonic acid, 4- or 6-acetylamino-2-aminophenol-6- or -4-sulphonic acid, 4-nitro-2-aminophenol-6-sulphonic acid, 3 : 4 : 6-trichloro-2-aminophenol, 5-nitro - 4 - methyl - 2 - aminophenol, 4 - nitro - 6 - chloro - 2 - aminophenol, 5 - ethylsulphonyl - 2 - aminophenol, 5 - nitro - 4 - ethylsulphonyl - 2 - aminophenol, 6-nitro-4-tert.-amyl-2-aminophenol, 4-acetyl-6-acetylamino-2-aminophenol, 2-methoxy-5-ethoxy-aniline, 2-aminobenzoic acid, 4- or 5-chloro-2-aminobenzoic acid and 5-nitro-2-aminobenzoic acid.  The metallization is preferably carried out using chromic or cobalt compounds in aqueous solution or suspension, possibly with the addition of solvents such as ethylene glycol or dioxan.  Alkali metal chromosalicylates are the preferred chroming agents.  Dyestuffs containing an o-alkoxy group are preferably metallized in formamide or ethylene glycol with chromic salts at temperatures of over 100 DEG  C.  Mixtures of dyestuffs of the above formula and mixtures of dyestuffs of the above formula with similar metallizable dyestuffs may also be metallized.  Metal complexes of the above formula which contain no groups dissociating acid in neutral water may be converted into the copper, vanadium, manganese, chromium, nickel, iron or cobalt compounds which may be used to dye cellulose lacquers or spinning solutions.  The metal complexes dye natural and synthetic polypeptide fibres in blue shades.  In examples, dyes are prepared from the following components and the chromium and cobalt complexes thereof are formed: diazo components:-4-chloro- or -nitro- or -methoxy-2-aminophenol, 4 - chloro - 2 - aminophenol - 6 - sulphonic acid, 4 : 6-dichloro-2-aminophenol, 6-nitro - 4 - chloro- or -methyl - 2 - aminophenol, 5-chloro- or -nitro-2-aminophenol, 5-nitro-4-chloro-2-aminophenol, 2 : 5-dimethoxy-aniline, 6 - nitro - 2 - aminophenol - 4 - sulphonic acid, 2-aminophenol-5-sulphonamide or -methylsulphone, 2-aminophenol-4-ethylsulphone, 4-nitro-or -chloro-6-acetylamino-2-aminophenol and 6 - acetylamino - 2 - aminophenol - 4 - methylsulphone; coupling components:-1 - acetylamino - 8 - naphthol - 6 - sulphamide or -sulphodimethylamide or -sulphonic acid phenylamide or -sulphomethylamide or -sulphonic acid-N-ethyl-anilide or -methylsulphone, 1-propionylamino - 8 - naphthol - 6 - sulphonic acid anilide or -sulphopropylamide, 1-ethoxyacetylamino-8-naphthol - 6 - sulphamide, 1 - carbomethoxyamino- or -carboethoxyamino-8-naphthol-6-sulphamide, 1 - methanesulphonylamino - 8 - naphthol-6-sulphonic acid morpholide, 1-p-toluenesulphonylamino - 8 - naphthol - 6 - sulphonic acid piperidide, 1-benzoylamino-8-naphthol-6-sulphonic acid ethanolamide or -phenylsulphone, 1 - ureido - 8 - naphthol - 6 - sulphamide, 1 - benzenesulphonylamino - 8 - naphthol - 6 - phenylsulphone, 1 - b  - chloropropionylamino - 8 - naphthol - 6 - sulphonic acid ethanolamide and 1 - ethylsulphonylamino - 8 - naphthol-6-sulphamide.  Reference has been directed by the Comptroller to Specifications 637,404, 667,168, 712,037, 736,034, 737,619, 743,583 and 774,884.