Patent GB-906806-A (GB)
Title: New 1:2-metal complexes of monoazo dyes containing halogenoacylamino groups
Inventor: BLACKHALL ALEXANDER
Filed: 1958-06-23
Abstract: 1-Trichloroacrylylamino- and -(b -chloropropionylamino)-7-naphthols, 1 - chloroacetylamino-4- and -6-naphthols, 2-chloracetylamino-6- and -7-naphthols, 3-o -chloroacetylamino-4-methylphenol, 1-(31-chloroacetylaminophenyl and 21-methyl-51-chloroacetylaminophenyl) -3-methyl-5-pyrazolone hydrochlorides are made by acylating the corresponding amine. 4-Chloroacetylamino-2-aminophenol is made by nitrating the corresponding 2-phenol and reducing the nitro compound thus formed. 4-N-methyl-N-chloroacetylamino-2-aminophenol is made in a similar fashion.  2-Aminophenol-4-sulphon-N-chloracetylamide and -N-methylchloracetylamide are made by acylating 2-nitrophenol-4-sulphonamide or its N-methyl derivative respectively and reducing the products. 5-Chloracetylaminoanthranilic acid is made by acylating 4-nitroaniline-3-carboxylic acid and reducing the product. 4-Chloracetylaminoanthranilic acid is made by treating 4-nitroanthranilic acid with chlorsulphonic acid, reducing the product to the amine, acylating and hydrolysing under acidic conditions.  4-Chloracetylamino-acetoacetanilide is made by treating p-nitroaniline with chlorsulphonic acid and treating the so-formed sulphamic acid in a fashion similar to that of the previous preparation to give 4-amino-chloracetanilide from which the required product is obtained on treatment with diketene.  All the products are dye intermediates (see Group IV(c)). Specifications 787,305, 885,814 and 885,815 are referred to.ALSO:The invention comprises dyes, free from sulphonic and carboxylic acid groups, and of formula <FORM:0906806/IV (b)/1> where A1 and A11 are substituted or unsubstituted phenylene or naphthylene residues, B1 and B11 are coupling component residues coupled in ortho or vicinal positions to metallisable groups, Z1 and Z11 are O or COO, D1 and D11 are O or NH, m is 1, 2 3 or 4, M is a metal atom, P is a cation, X is NH, N alkyl, SO2NH or SO2 N alkyl and Y is halogenoalkyl or -hydroxyalkyl or trichlorovinyl, provided that A1 and A11 each have not more than one X.COY group and that when they each stand for a phenylene or a substituted phenylene radical containing a sulphonamido or a mono-substituted sulphonamido group -B1-D1 and -B11-D11 do not each represent the residue of a 2-naphthol carrying one of the X.COY groups in the 8-position of the naphthalene ring.  The dyes are made by conventional metallisation processes or by acylating appropriate metal complexes with an acylating agent derived from an acid of formula Y.COOH.  The groups X.COY are directly attached to aryl rings in A1, A11, B1 and B11.  M is specified as Fe, Al, V, Co, Cr and Zr, Co and Cr being preferred.  P is specified as K, Na and NH4. Representative of specified values for Y are dichloromethyl, g -chloro-a -propyl and a -hydroxy-b -chloroethyl.  Preferably Y is a halomethyl group, e.g. bromomethyl and especially chloromethyl. Illustrative of indicated substituents, other than X.COY groups, which may be present in A1 and A11 are nitro, acylamino, alkyl, alkoxy, alkylsulphonyl, halogen, sulphamoyl, N-b -hydroxyethylsulphamyl, N,N-diethylsulphamoyl, cyano and trifluoromethyl.  Indicated for B1 and B11 are acetoacetarylides, 5-pyrazolones, phenols or naphthols and they may contain substituents, other than X.COY groups, such as nitro, halogen, alkyl, alkoxy, acylamino, sulphamoyl, substituted sulphamoyl and alkylsulphonyl groups.  Representative of specified diazo components used in the preparation of the metal-free dyes are anthranilic acid, 4-nitro- and -chloracetylamino-anthranilic acid, 2-aminophenol, 4-methyl and -chloro-2-aminophenol, 2-aminophenol-4-sulphon-N-phenylamide, 2-aminophenol- 4-sulphon-N-benzene-sulphonamide, 2-aminophenol - 4 - sulphon-N-acetylamide, 4-chloracetylamino-2-phenol, 6-chloro-2-aminophenol- 4-methylsulphone and 2-aminophenol- 4-propylsulphone.  Representative of specified coupling components are p-acetoacetaminoo -chloracetanilide, 3-chloracetylamino-4-methylphenol, 1-(21-methylphenyl)-3-methyl-5-pyrazolone, 1-acetyl-, -trichloro-acryloyl-, -bromacetyl-, -b -chloropropionyl-and -carboisopropoxy-amino-7-naphthols, 2-naphthol-6-sulphonamide and 2-naphthol.  The complexes colour nitrogenous materials such as natural and regenerated protein fibres and polyamide fibres, from a neutral or slightly acid dye-bath.  Disperse processes are used when the dyes are insoluble.  Numerous examples are provided of the preparation of the dyes and their use in colouring wool in a variety of colours.  The dyes of the Provisional Specification are free from sulphonic acid groups but otherwise the above proviso does not operate, m may also be 5 and 6, X a direct link or O and S and Z1 and Z11 an alkoxy group. 1,1-Metal complexes of the dyes are also described and the conversion of the 1,1-complexes to the 1,2-complexes.  Specifications 637,404, 683,891, 787,305, 885,814 and 885,815 are referred to.