Patent GB-827655-A (GB)
Title: Benzothiazole azo compounds containing a reactive methylene coupling component, metal complexes thereof and materials dyed or coloured therewith
IPC: C07D277/82
Filed: 1956-02-27
Abstract: Trifluoroacetoacetanilide is prepared by reacting aniline with ethyl trifluoracetoacetate in the presence of triethanolamine, ethanol, and xylene.ALSO:The invention comprises monoazo dyestuffs of formula <FORM:0827655/IV(c)/1> wherein Ar is a substituted or unsubstituted o-phenylene radical, E is -CN, R.NH.CO-, or Q1-CO-, and E1 is respectively X.Co-, Q.CO-, and Y.CO-; and in the above groups R is a substituted or unsubstituted phenyl or naphthyl radical, Q1 is CH3O- or C2H5O-, X is a substituted or unsubstituted phenyl, naphthyl, phenylamino or styryl radical and Q and Y are -CF3 or a substituted or unsubstituted phenyl radical and Q also may be CH3-; and metal complexes thereof.  The dyes are prepared by diazotizing a suitable 2-aminobenzothiazole and coupling with a reactive methylene compound having the groups E and E1, as defined above, linked to the methylene group.  Specified diazo components other than those in examples are 2-amino-6-ethyl- or -n-propyl or -n-butyl-sulphonyl-, 2-amino-6-N-methyl- or -n-propyl- or -n-butyl-sulphon-amido-, 2-amino-6-n-propoxy- or -n-butoxy-, 2 - amino - 6 - methyl- or -ethyl- or -n-propyl- or -n-butyl-, 2-amino-6-b -hydroxyethyl-or -g -hydroxypropyl- or -d -hydroxybutyl-, 2-amino-6-acetylamino- or -n-propionylamino- or -n-butyrylamino-, 2-amino-6-thiocyano- and 2 - amino - 4:7 - diethoxy - benzothiazole. Specified coupling components other than those in examples are trifluoroacetoacet-2-methoxyor -methyl- or -chloro-anilide, trifluoracetoacet4-chloro- or -nitro-anilide, cyanoacet-2- or -4-methyl- or -chloro-anilide, p-nitro- or -o- or p-chloro- or -o-methyl- or -methoxy-benzoyl-acetonitrile, methyl p - nitrobenzoyl - acetate, methyl or ethyl benzoylacetate, and p-nitro- or o - chloro - or-methyl - cinnamoylacetonitrile.  Specified metals which may be used to form the metal complexes are nickel, cobalt, copper, chromium, manganese, iron and vanadium and a wide variety of salts of these metals are specified as metallizing agents.  The metallization is preferably carried out in organic solvents such as cellulose acetate, cellulose acetate-propionate, polyacrylonitriles, polyamides, ethylene glycol monomethyl ether and formamide.  The dyes and their metal complexes may be used to dye cellulose esters, polyacrlonitriles, polyamides, polyesters and silk or wool in yellow, orange, red and brown shades.  In examples: (1) 2-amino - 6 - methylsulphonyl - benzothiazole is dissolved in concentrated sulphuric acid and diazotized by the addition of sodium nitrite and the mixture is added to a cooled solution of acetoacet-2-methyl- or -methoxy-anilide or acetoacet - 2:4 - dimethylanilide in propionicacetic (1:5) acids to give a yellow monoazo dye; (2) 2-amino-6-methoxybenzthiazole is diazotized with sodium nitrite in a mixture of sulphuric, acetic and propionic acids and the mixture is coupled with a solution of acetoacetanilide or benzoylacetonitrile in propionicacetic (1:5) acids to give the monoazo dyestuff and 2-amino-4-methoxybenzothiazole and benzoylacetonitrile are also used in the reaction; (3) 2-amino-6-nitrobenzothiazole ---> benzoylacetonitrile as in (1); (4) the dyestuffs obtained in the above examples are metallized by heating in ethylene glycol monomethyl ether, formamide or acetone under alkaline conditions with nickel acetate or thiocyanate; (5) a cellulose acetate fabric is dyed with the dyestuff 2-amino-6-methylsulphonylbenzthiazole ---> acetoacet-2-methoxyanilide padded with a solution of nickel thiocyanate and treated in the usual way to form the nickel complex of the dye on the fibre; (6) as in (5) the dye 2-amino-6-methoxybenzthiazole ---> acetoacetanilide is treated with cobalt thiocyanate on a cellulose acetate fibre; (7) as in (5) but the dyed fabric is treated with a mixture of copper sulphate and a ureaformaldehyde resin.  A Table is given wherein the preparation of dyes from the following additional components and their conversion into metal complexes is specified; diazo components:-2 - aminobenzothiazole, 2 - amino - 6-cyano- or -N-ethylsulphonamido- or -chloro-or - ethoxy - or - methylthio - or - trifluoro - methyl - benzothiazole, 2 - amino - 5 - meth - oxybenzothiazole, 2-amino-4:7 - or -5:6 - dimethoxybenzothiazole and 2-amino-4:6 - dimethylbenzothiazole; coupling components:-acetoacet-4-chloro- or -methoxy- or -nitro- or -b -hydroxyethyl-anilide, acetoacet - 2:4 - dichloroanilide, acetoacet - 3 - methylolanilide, 2 - acetoacetonaphthalide, cyanoacet - 4 - nitroanilide, benzoylacet - (4 - benzamido - 2:5 - dimethoxy) - anilide, 2 - cyanoacetonaphthalene, m - nitrobenzoylacetonitrile and ethyl p-nitro-benzoyl-acetate, and methyl trifluoro-aceto-acetate.  Specifications 764,296, 764,297, 764,298, 781,435 and 816,396 are referred to.ALSO:Metal complexes of monazo dyestuffs containing benzothiazole residues (see Group IV (c)) are prepared on cellulose ester materials by adding the metallizing agent to the dope, spinning or casting, a yarn, fibre, or film, and then treating the fibre &c. with the nonmetallized monoazo dye.  The metallizing agent may be a salt of chromium, cobalt, copper, iron, manganese, nickel, or vanadium.  In an example, a cellulose acetate yarn containing chromic chloride which has been incorporated in the spinning dope is dyed with the dyestuff 2-amino - 6 - methoxybenzthiazole --> acetoacetanilide and the metal complex is formed on the yarn. Alternatively, the metallized or non-metallized organic azo compound may be added to a cellulose ester dope which is then formed into filaments or films, and these may be treated to convert the dye to the metal complex if required.  Specification 816,396 is referred to.