Patent GB-978358-A (GB)
Title: Reactive metallised azo dyestuffs
Inventor: BLACKHALL ALEXANDER
IPC: C09B62/032
Filed: 1962-02-07
Abstract: 1-(41-Amino -31- carboxyphenyl)-4, 5-dichloropyridaz -6- one is prepared by diazotising sodium 5-amino -2- nitrobenzoate, reducing the diazonium compound with stannous chloride and concentrated hydrochloric acid, adding mucochloric acid, removing the precipitated hydrazone of mucochloric acid by filtration, treating it with sulphuric acid to yield 1-(41-nitro -31- carboxyphenyl)-4, 5-dichloropyridazone which is reduced by refluxing in a mixture of aqueous ethanol iron filings and acetic acid.  1-[31-(411, 511-dichloropyridaz-611-on-111-yl)-phenyl] -3- methyl -5- pyrazolone is prepared by diazotising 1-(31-aminophenyl)-4, 5-dichloropyridaz-6-one, reducing the diazonium compound with stannous chloride and hydrochloric acid to the corresponding hydrazine compound and reacting this in aqueous medium with acetoacetamide.  3-(41, 51-dichloropyridaz-61-on-11-yl) acetoacetanilide is prepared by reacting 1-(31-aminophenyl)-4, 5-dichloropyridaz-6- one with diketene.  Specification 881,616 is referred to.ALSO:The invention comprises the metallized azo dyes which in the form of the free acids are of formula <FORM:0978358/C4-C5/1> wherein B1 and B11 are coupling component radicals coupled in ortho position to a hydroxy or amino group; Z1 and Z11 are -O- or -COO-; D1 and D11 are -O- or -NH-; M is a cobalt or chromium atom; n is 1, 2 or 4; X is a monohalo-1 : 3 : 5-triazinylamino, dihalopyrimid - (2 - or 4 - ) ylamino, trihalopyrimid - (2 - or 4 - ) ylamino, 5 - cyanodihalopyrimid-(2- or 4-)ylamino, 4 : 5-dihalopyridaz - 6 - on - 1 - yl - benzenesulphonyl-amino, 4 : 5 - dihalopyridaz - 6 - on - 1 - yl or 4 : 5 - dihalopyridaz - 6 - on - 1 - ylbenzenecarbonylamino group which is attached directly to a carbon atom of the benzene rings A1 and A11 or to a carbon atom of a benzene or naphthalene ring present in B1 or B11, wherein halo is chloro or bromo and wherein the rings A1 and A11 may be further substituted provided that A1, A11, B1 and B11 are free from sulphoni and carboxylic acid groups.  The dyes may be prepared by treating a metallized azo dye of the above formula but wherein X is an acylatable amino group with an equimolar amount of a di- or tri-halotriazine, 2 : 4 : 6-trihalopyrimidine, 2 : 4 : 5 : 6-tetrahalopyrimidine, 2 : 4 : 6-trihalo - 5 - cyanopyrimidine, 4 : 5 - dihalopyridaz-6- on - 1 - ylbenzenesulphonyl chloride or 4 : 5 - dihalopyridaz - 6 - on - 1 - ylbenzenecarbonyl chloride. When a tri-halotriazine is used as acylating agent, the product is further reacted with ammonia or an amine, alcohol or phenol to replace a halogen atom by an amino, substituted amino, alkoxy or aryloxy group. The dyes may also be prepared by treating 2 moles of one or two different monoazo dyes of formula <FORM:0978358/C4-C5/2> wherein A1, B1, D1 and Z1 are as defined above, m is 0, 1 or 2 and X1 is a 4 : 5-dihalopyridaz-6-on - 1 - yl, 4 : 5 - dihalopyridaz - 6 - on - 1 - ylbenzene - sulphonylamino or 4 : 5 - dihalopyridaz - 6 - on - 1 - yl - benzenecarbonylamino group linked as specified above with 1 mol. of a chroming or cobalting agent, provided that at least one of the monoazo compounds contains at least one X1 group. Finally, the dyes may be prepared by reacting an azo dye of formula <FORM:0978358/C4-C5/3> wherein A1, B1, D1 and Z1 are as defined above with a 1 : 1-chromium complex of the same or a different azo dye of the formula, the two azo dyes containing 1, 2 or 4 X groups.  The metallized azo dyes give brown and grey shades on cellulose fibres in the presence of an acid-binding agent.  They may also be used to colour natural and synthetic polyamide materials, in particular wool, in yellow, orange, red, violet and grey shades.  The preparation of the dyes is described in numerous examples.  The Provisional Specification refers to metallized azo dyes of the above formula wherein A1 and A11 are naphthalene residues and specifies further reactive residues X of the halopyrimidine and halotriazine series. No additional specific dyes are disclosed.  Specifications 822,047, 917,780 and 924,660 are referred to.