Patent GB-926377-A (GB)
Title: Dyes of the tetrazaporphin series and their production
Inventor: ROHLAND WERNER
Filed: 1960-08-08
Abstract: The sulphuric semiester of m- or p-amino-b -hydroxypropionyl-anilide is made by esterifying with chlorosulphonic acid m- or p-amino-b -hydroxypropionyl-anilide obtained by reducing m- or p-nitro-b -hydroxypropionyl-anilide. These are prepared by hydrolysing m- or p-nitro-b -formoxy- or acroyloxy-propionyl-anilides obtained by condensing m- or p-nitraline with b -formoxypropionyl or b -acroyloxypropionyl chlorides.  The sulphuric acid semiester of p-amino-b -hydroxypropionyl-anilide is also made by treating with sulphuric acid p-amino-b -acetoxypropionyl-anilide prepared by reduction of p-nitro-b -acetoxypropionyl-anilide obtained by condensing p-nitraniline with b -acetoxypropionyl chloride.ALSO:The invention comprises dyes of the formula:-Z-(D)n where Z is a tetrazaporphin radical which may be further substituted, n is an integer from 1 to 4 and D is a radical of the formula:- <FORM:0926377/IV(a)/1> where R1 is hydrogen or the radical of sulphuric acid or phosphoric acid, and particularly dyes which in the form of the free acids have the formula:- <FORM:0926377/IV(a)/2> where A is a tetrazaporphin radical, n is an integer from 1 to 4, m is an integer from 0 to 4, (n+m) is an integer from 1 to 8, D is the group HO3S-O-CH2-CH2CO.NH-and E is a direct linkage, an alkylene group, a <FORM:0926377/IV(a)/3> group, a -CO-NH-Q- group or an -SO2-NH-Q-group where G is arylene and Q is alkylene or arylene which may contain sulphonic acid groups.  The tetrazaporphin radicals include di- and tribenzotetrazaporphins and metal or metal-free phthalocyanines.  The dyes are made by treating an amide of the formula:- <FORM:0926377/IV(a)/4> where R11 is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical and Y is a tetrazaporphin radical which may contain up to three additional <FORM:0926377/IV(a)/5> groups and other substituents, in the presence of an at least stoichiometric amount of water with ammonia, an amine, a hydrazine or hydroxylamine and if desired esterifying the product of the formula <FORM:0926377/IV(a)/6> with sulphuric acid or phosphoric acid or, when R1 is to be the radical of sulphuric acid, by treating the amide of the Formula VII(a) with 90 to 100% sulphuric acid at temperatures between 0 DEG  and 100 DEG C.  The dyes may also be made by reacting tetrazaporphins having n exchangeable halogen atoms, e.g. as chlormethyl, sulphonic acid halide or carboxylic acid halide groups, with amines of the formula:- <FORM:0926377/IV(a)/7> where Y1 is an aryl radical containing an acylatable amino group. Examples are given.  The amides of the Formula VII(a) above are made by condensing a tetrazaporphin containing amino groups with b -acyloxypropionic acid halides such as b -formoxy-, b -acetoxy- or b -acroyloxy-propionyl chlorides.  The dyes dye and print foils, films and textile materials of wool, silk, polycaprolactam, linear polyamides, natural or regenerated cellulose, leather and paper in blue to green shades.  The dyes containing sulphuric acid or phosphoric acid ester groups are reactive with materials of cellulose and polyvinyl alcohol.