Patent GB-806709-A (GB)
Title: Monoazo dyestuffs of the benzene-azo-pyrazolone series and metal complexes thereof
IPC: C09B45/14
Filed: 1956-04-20
Abstract: Compounds of formula (enol form) <FORM:0806709/IV (b)/1> wherein Y is an alkyl, aryl, CONH2, CONH (alkyl), CON(alkyl)2 or CO.O.alkyl group, Z is hydrogen or a substituent other than a sulphonic or carboxylic acid group, and R1 is a methylene or o-arylene radical may be prepared by converting heterocyclic ether sulphones containing amino groups (cf. Specification 753,261) via their diazo compounds into the corresponding hydrazines and condensing the latter with, for example, acetoacetic, benzoylacetic or oxalacetic acid esters to give the corresponding pyrazolones.  They are used as coupling components in the manufacture of azo dyestuffs (see Group IV (c)).  Specified compounds are of the above formula wherein Y=CH3, Z=H, Cl or CH3 and R1=CH2; Y=CONH2, CON(CH3)2, CO.O.C2H5 or C6H5, Z=H and R1=CH2; Y=CH3, Z=H and R1=4-chloro-1 : 2-phenylene.  Specification 731,495 also is referred to.ALSO:The invention comprises monoazo dyestuffs of formula <FORM:0806709/IV (c)/1> wherein R is a radical of the benzene series free from sulphonic acid and non-complex forming carboxylic acid groups, X is a group capable of forming a metal complex ortho to -N = N-, Y is alkyl, aryl, -CONH2, CONH(alkyl), CON (alkyl)2 or CO.O.alkyl, Z is hydrogen or a substituent other than a sulphonic or carboxylic acid group and R1 is methylene or an o-arylene radical; and the metal complexes thereof.  The dyestuffs are prepared by coupling a diazotized aminobenzene, which is substituted as defined above with a pyrazolone of formula <FORM:0806709/IV (c)/2> wherein Y, Z and R1 are as defined above.  The preferred metal complexes are the chromium and cobalt complexes.  They are prepared by treating the dyestuffs with chromium- or cobalt-yielding agents in known manner, preferably so as to yield 2 : 1 complexes.  A mixture of two different dyestuffs of formula (I) or a dyestuff of formula (I) and another known metallizable monoazo dyestuff may also be metallized, possibly by formation of the 1 : 1 complex of one of the dyestuffs and reaction of this complex with the other dyestuff.  Specified components in addition to those specified in examples are: diazo components: 2-aminophenol, 1-amino-2 - hydroxy - 4 - or 5 - chlorobenzene, 1 - amino-2 - hydroxy - 3 : 5 - dichloro - or dinitro - benzene, 1 - amino - 2 - hydroxy - 3 - nitro - or chloro - 5 - nitro - or chloro - benzene, 1-amino - 2 - hydroxy - 3 - methyl - 5 - nitrobenzene, 1 - amino - 2 - hydroxybenzene - 5 - sulphopiperidide or sulphomorpholide or sulphoanilide or sulphoethylamide, 1-amino-2-hydroxy-3-chlorobenze - 5 - sulphonamide and anthranilic acid - sulphonamides; coupling components: compounds of formula (II) wherein Y = CONH2 or CO.OC2H5, Z = H and R1 = CH2.  The metal complexes may be used to colour resins, lacquers and plastic masses and to dye leather, wool and synthetic polyamides and polyurethanes. They dye wool in red or yellow shades.  In examples: (1) the diazo compound from 1 - amino - 2 - hydroxy - or methoxy - 5-sulphonamide, 1 - amino - 2 - hydroxy - 4 - or 5 - nitrobenzene, 1 - amino - 2 - hydroxy - 5-methyl - 3 - nitrobenzene, 1 - amino - 2 - hydroxybenzene - 5 - ethyl - or n - propyl - sulphone, 3 - amino - 4 - hydroxy - diphenylsulphone - (1 : 11), 1 - amino - 2 - hydroxybenzene-5 - sulpho - methylamide or dimethylamide, 1-amino - 2 - hydroxybenzene - 5 - sulpho - methyl-b  - hydroxyethylamide, 1 - amino - 2 - hydroxybenzene - 4 - sulphonamide or sulphomethylamide, 1 - amino - 2 - hydroxy - 5 - chlorobenzene - 3 - sulphonamide, anthranilic acid or 4-amino - 5 - hydroxybenzoxathiol - S - dioxide is coupled with the compound of formula (II) wherein Y = CH3, Z = H and R1 = CH2, the chromium and cobalt complexes of the dyestuffs being prepared; (2) the diazo compound from 1 - amino - 2 - hydroxy - or methoxybenzene - 5 - sulphonamide is coupled with a compound of formula (II) wherein Y = CH3, Z = Cl or CH3 and R1 = CH2 or Y = phenyl, Z = H and R1 = CH2 or Y = CON(CH3)2, Z = H and R1 = CH2 or Y = CH3, Z = H and R1\t = 4-chloro-1 : 2-phenylene and the cobalt and chromium complexes of the dyestuffs are prepared; (3) the chromium complex of a mixture of dyestuffs, i.e. 1-amino-2-hydroxybenzene-5-sulphonamide --> compound of formula (II) wherein Y = CH3, Z = Cl and R1 = CH2 and 1 - amino - 2 - hydroxy - 5 - nitrobenzene --> compound of formula (II) wherein Y = CH3, Z = H and R1 = CH2 is prepared; (4) the cobalt complex of a mixture of dyestuffs as in (3), except that the diazo compound of the second dyestuff is 1-amino-2-hydroxybenzene-5-sulphodimethylamide, is prepared; (5) the chromium and cobalt complexes of a mixture of dyestuffs, i.e. 1 - amino - 2 - hydroxybenzene-5 - ethylsulphone --> compound of formula (II) wherein Y = CH3, Z = H and R1 = CH2 and 1 - amino - 2 - hydroxy - 5 - nitrobenzene --> 2 - hydroxy - 8 - methylsulphonylamino-naphthalene are prepared.  Specifications 681,653, [731,495, 753,261] [both in Group IV (b)], 758,016 and 766,554 are referred to.