Patent GB-917454-A (GB)
Title: Improvements relating to quaternary ammonium salts of diazoamino compounds and theiruse as dyestuffs
IPC: C09B26/06
Filed: 1959-06-03
Abstract: Diazoamino compounds of tautomeric formulae <FORM:0917454/IV (b)/1> <FORM:0917454/IV (b)/2> <FORM:0917454/IV (b)/3> wherein X is a divalent radical completing a 5- or 6-membered ring, R is an isocyclic aryl radical which may be substituted and n is 0 or 1 are prepared by condensing diazo compounds of arylamines R-NH2 with amines of formula HO-Z.  They are used as intermediates in the preparation of dyes (see Group IV(c)).  In an example p-nitroaniline is diazotised and the diazo compound reacted with 2-aminobenzthiazole to give 1,3-[benzthiazolyl-(21)-p-nitrophenyl]-triazene.  The following are also prepared in examples:- 1,3-[61-methoxybenzthiazolyl-(21) -m-nitrophenyl]-triazene, 1,3-[61-acetylaminobenzthiazolyl - (21) - o - nitrophenyl] - triazene, 1,3-[31-methyl-21,31-dihydro benzthiazolylidene - (21) - p - methylsulphonylphenyl]-triazene, 1,3-[thiazolyl - (21) - p - nitrophenyl]-triazine and 1,3-[pyridyl-(21)-p-nitrophenyl]-triazene and 1,3-[pyridyl-(21)-p-nitrophenyl]-triazene.  Many alternative reactants are specified.ALSO:The invention comprises water-soluble dyes of formula <FORM:0917454/IV (b)/1> wherein X is a divalent radical which completes the nitrogen-containing ring into a 5- or 6-membered ring, R is an isocyclic aryl radical which may be substituted, n is 0 or 1, Z is the residue of a primary aliphatic alcohol with 1 to 5 carbon atom or of a benzyl alcohol which may be substituted in the benzene nucleus and Y\s8 is the anion derived from an alkylating agent or the anion introduced by interaction of the primarily obtained dye salt with a metal salt or the anionic group of a double salt derived from said anions and a metal salt, which anions and anionic groups are equivalent to the dye cation.  The dyes give yellow to orange shades on polyacrylonitrile fibres.  They ar prepared by treating 1 mol of a diazomino compound of tautomeric formulae <FORM:0917454/IV (b)/2> (see Group IV(b)) with 2 mols of a reactive ester of an alcohol (Z-OH) and possibly adding a metal salt or by using as starting material a diazoamino compound already containing one Z substituent at the ring N atom or the N atom adjacent R and 1 mol of an ester of Z-OH.  In examples: (1) 1,3-[benzthiazolyl- (21)-p-nitrophenyl]- triazine is treated with an excess of dimethyl sulphate and the product precipitated as the zinc chloride double salt (the same dye is also prepared by using 1 mol of dimethyl sulphate, separating the mono-N-methyl compound and treating this with an excess of dimethyl sulphate); (2) as in (1) using 1,3-[61-methoxy-benzthiazolyl-(21) -m-nitrophenyl]-triazene and diethyl sulphate or 1,3-[thiazolyl-(21)-p-nitrophenyl]-triazene and dimethyl sulphate; (3) 1,3-[61-acetylaminobenzthiazolyl- (21) -o-nitrophenyl]-triazene is treated with dimethyl sulphate; (4) 1,3-[31-methyl- 21, 31-dihydrobenzthiazolylidene-(21) -p-methylsulphonylphenyl]-triazene is treated with methyl or ethyl iodide and the dye salt is precipitated with sodium iodide; (5) as in (4) using 1,3-[pyridyl-(21)- p-nitrophenyl]-triazene and methyl iodide.  Many alternative reactants are specified.