Patent GB-773790-A (GB)
Title: New metal-containing polyazo dyestuffs of the stilbene series
IPC: C09B45/24
Filed: 1953-12-16
Abstract: The invention comprises metal-containing polyazo dyestuffs of the stilbene series of formula <FORM:0773790/IV(b)/1> wherein R is a benzene, naphthalene or diphenyl radical which may be further substituted by halogen atoms, alkyl, alkoxy, carboxylic or sulphonic acid groups, R1 is a benzene or naphthalene radical which may be further substituted by halogen atoms, hydroxy, alkyl, alkoxy, carboxylic or sulphonic acid groups, R2 is a phenylene radical which may be further substituted by halogen atoms, alkyl, alkoxy, nitro, carboxylic acid, sulphonic acid or sulphonamide groups, a is a group capable of taking part in metal complex formation and present ortho to -azo-, w is a hydrogen atom or a -N=N- aryl radical of the benzene series, Me is a heavy metal atom and -azo- and -azo1-are in the 1 : 4 - or 4 : 41 - positions of R. The dyestuffs are prepared by coupling 1 mol of the diazo compound from an aminodisazo compound of the formula <FORM:0773790/IV(b)/2> wherein R and R1 are as defined above and -azo- and -N=N- stand in the 1 : 4 - or 4 : 41 - positions of R, with one mole of a monoazo compound of the formula <FORM:0773790/IV(b)/3> wherein R2 and a are as defined above, and treating the polyazodyestuff thus obtained with a metal-yielding agent. Alternatively the monoazo compound of formula III may be used in the form of its metal complex compound.  A further method of preparing the dyestuff is by coupling 1 mol of the diazo compound from an aminodisazo compound of formula II, first with 1 mol of resorcinol, and then coupling the resultant trisazo compound with 1 mol of the diazo compound from an aromatic amine, b-R2-NH2, wherein R2 is as defined above and b is a metallizable group ortho to -NH2, and treating the polyazo dyestuff thus obtained with a metal-yielding agent.  When b is a hydroxy group it can be free or can be closed by an alkyl - or arylsulphonyl radical which must be split off before metallization of the final product.  The polyazo dyestuff obtained as above may be further coupled with at most 1 mol of a diazotized aminobenzene before or after the treatment (if any) with a metallizing agent.  The metallization processes are carried out by known methods using copper-, chromium-, nickel- and cobalt-yielding agents.  The compounds of formula II may be prepared by condensing a 4 : 41 - dinitro - 1 : 11 - stilbene - 2 : 21 - disulphonic acid with an appropriate aminomonoazo compound and reducing the nitro group in the resultant product to amino.  Alternatively the diazo compound from 4 - nitroor - acylamino - 41 - amino - 1 : 11 - stilbene - 2 : 21 - disulphonic acid is coupled with an amine of the benzene or naphthalene series coupling para to amino, the resultant aminomonoazo compound is diazotized and coupled with a hydroxy compound of the benzene or naphthalene series, the hydroxy group is alkylated if desired, and finally the nitro or acylamino group is converted to amino.  The compounds of formula III are prepared by diazotizing suitable amines of the benzene series and coupling them with resorcinol.  The metallized polyazo dyestuffs dye and print cotton, regenerated cellulose, wool, silk, artificial nitrogenous fibres and leather in brown shades.  In examples: (1) aminodisazo dyestuff of formula II are diazotized and coupled with metal complexes of monoazo dyestuffs of formula III, some of the products being coupled with a diazotized aminobenzene 1 - amino - 4 - nitrobenzene - 2 - sulphonic acid is specified).  Specified aminodisazo dyestuffs (only the grouping R1 - azo - R - H is given below) are:- 1 : 11 - azobenzene (4)-41 - sulphonic acid, 2 - methyl - 1 : 11 - azobenzene (4) - 31 - sulphonic acid, 1 : 11-azobenzene (4) - 31 - or - 41 - carboxylic acid, 61 - chloro - 1 : 11 - azobenzene (4) - 31 - sulphonic acid, 1 - phenylaxo - naphthalene (4) - 6 : 41 - disulphonic acid, 1 - naprthyl (21) - azo - 2 - methylbenzene (4) - 41 : 81 - disulphonic acid, 41 - hydroxy - or - methoxy - 1 : 1 -azobenzene (4) - 2 - sulphonic acid, 41 - (411 - methoxy) - phenylazo - 1 : 11 - diphenyl (4) - 31 - sulphonic acid, 2 - chloro - 211 - methyl - 1 : 11 - azobenzene (4) - 5 -sulphonic acid, 2 - methoxy - 1 : 11 - azobenzene (4) - 41 - sulphonic acid, and 3 - carboxy - 1 : 11 - azobenzene (4) - 41 - sulphonic acid; specified monoazo dyestuffs of formula III used in the form of their copper, chromium, cobalt and nickel complexes are:- 2 : 21 : 41 - trihydroxy - 1 : 11 - aozbenzene - 5 - sulphonic acid or - sulphonamide or - sulphonic acid-(b  - hydroxy - or methoxy) - ethylamide or - sulphonic acid - (g  - hydroxy - or methoxy) - propylamide, 2 : 21 : 41 -trihydroxy - 5 - nitro - 1 : 11 - azobenzene - 3 - sulphonic acid, 2 : 21 : 41 - trihydroxy - 5 - or - 3 - chloro - 1 : 11 - azobenzene - 3-or - 5 - sulphonic acid, 2 : 21 : 41 - trihydroxy - 3 - carboxy - 1 : 11 - azobenzene - 5 - sulphonic acid, 2 : 5 - dimethoxy - 21 : 41 - dihydroxy - 1 : 11 - azobenzene - 4 - sulphonic acid, and 2 - methoxy - 5 - methyl - 21 : 41 - dihydroxy - 1 : 11 - azobenzene - 4 - sulphonic acid; (2) the aminodisazo dyestuff of formula II wherein the group R1 - azo - R - H is 1 : 11 azobenzene (4) - 41 - sulphonic acid is diazotized and coupled with resorcinol, the resultant triazo dyestuff being coupled with the diazo compound from 2 - amino - phenol - 4 - sulphonic acid and the tetrazo dyestuff coppered; (3) as in (2) but using as the second diazo component 1 - amino - 2 - [41 - methylphenyl (11) - sulphonyloxy] - benzene - 5 - sulponic acid, the 4 - methylphenyl (1) - sulphonyl group being split off by beating the final dyestuff in with aqueous sodium hydroxide before coppering.